U.S. patent number 5,827,927 [Application Number 08/645,914] was granted by the patent office on 1998-10-27 for macromonomers having reactive end groups.
This patent grant is currently assigned to Maxdem Incorporated. Invention is credited to Robert R. Gagne, Neil H. Hendricks, Matthew Louis Marrocco, III, Mark Steven Trimmer.
United States Patent |
5,827,927 |
|
October 27, 1998 |
**Please see images for:
( Certificate of Correction ) ** |
Macromonomers having reactive end groups
Abstract
A soluble rigid-rod macromonomer is provided which has the
following formula: ##STR1## wherein each A.sub.1, A.sub.2, A.sub.3,
and A.sub.4, on each monomer unit, independently, is C or N, and
each G.sub.1, G.sub.2, G.sub.3, and G.sub.4, on each monomer unit,
independently, is H or a solubilizing side group, provided that at
least one monomer unit has at least one solubilizing side group.
The solubilizing side groups provide the macromonomers with a
solubility of at least 0.5% by weight in the solvent system from
which they are formed. E is a reactive end group, and the
macromonomer has an average degree of polymerization, DP.sub.n,
greater than 6. Such macromonomers are chemically incorporated into
polymer systems to provide stronger stiffened polymers.
Inventors: |
Gagne ; Robert R. (Pasadena,
CA), Marrocco, III; Matthew Louis (Santa Ana, CA),
Trimmer; Mark Steven (Pasadena, CA), Hendricks; Neil H.
(Brea, CA) |
Assignee: |
Maxdem Incorporated (San Dimas,
CA)
|
Family
ID: |
25002904 |
Appl.
No.: |
08/645,914 |
Filed: |
May 14, 1996 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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331144 |
Oct 27, 1994 |
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746917 |
Aug 19, 1991 |
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Current U.S.
Class: |
525/143; 528/128;
528/225; 528/223; 528/154 |
Current CPC
Class: |
C08L
67/00 (20130101); C08G 73/0627 (20130101); C08G
73/0633 (20130101); C07C 255/56 (20130101); C08G
85/00 (20130101); C08G 8/28 (20130101); C08F
290/14 (20130101); C08G 69/02 (20130101); C07D
303/36 (20130101); C07D 295/192 (20130101); C08G
64/06 (20130101); C08L 71/126 (20130101); C08L
69/00 (20130101); C08L 67/02 (20130101); C08G
73/0638 (20130101); C07D 207/404 (20130101); C08G
69/20 (20130101); C08G 73/0622 (20130101); C08G
69/36 (20130101); C08F 290/141 (20130101); C08G
61/00 (20130101); C07C 225/22 (20130101); C07D
303/22 (20130101); C08G 61/02 (20130101); C08G
63/181 (20130101); C08G 63/6856 (20130101); C08G
69/26 (20130101); C08G 73/18 (20130101); C07D
303/46 (20130101); C08G 64/12 (20130101); C07C
225/16 (20130101); C07D 207/452 (20130101); C07D
209/76 (20130101); C07C 235/84 (20130101); C08F
290/06 (20130101); C08G 69/32 (20130101); C08L
85/00 (20130101); C08L 67/00 (20130101); C08L
2666/02 (20130101); C08L 67/02 (20130101); C08L
2666/22 (20130101); C08L 69/00 (20130101); C08L
2666/02 (20130101); C08L 69/00 (20130101); C08L
2666/22 (20130101); C08L 71/126 (20130101); C08L
2666/02 (20130101); C07C 2603/18 (20170501); C08G
2261/312 (20130101); C07C 2602/06 (20170501) |
Current International
Class: |
C08G
73/18 (20060101); C08G 73/06 (20060101); C08F
290/00 (20060101); C08G 85/00 (20060101); C08G
8/28 (20060101); C08L 67/02 (20060101); C08L
67/00 (20060101); C08L 69/00 (20060101); C08L
85/00 (20060101); C08G 8/00 (20060101); C08G
61/02 (20060101); C08G 61/00 (20060101); C08G
69/02 (20060101); C08G 69/20 (20060101); C08G
69/36 (20060101); C08G 69/32 (20060101); C08G
73/00 (20060101); C08G 69/00 (20060101); C08G
69/26 (20060101); C08F 290/14 (20060101); C08F
290/06 (20060101); C08F 008/00 () |
Field of
Search: |
;525/143
;528/128,154,223,225 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0436111 |
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Nov 1920 |
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EP |
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0130056 |
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Jan 1985 |
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EP |
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3821567 |
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Dec 1989 |
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DE |
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1259030 |
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Oct 1989 |
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JP |
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2113023 |
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Apr 1990 |
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JP |
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0928576 |
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Jun 1963 |
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GB |
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WO9005754 |
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May 1990 |
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WO |
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WO9102764 |
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Mar 1991 |
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WO |
|
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of Polyarylenequinones," Vysokomol. soyed., A13: No. 5, 1009-1017,
1971. .
Organic Chemistry 3rd Ed. Morrison and Boyd Allyn and Bacon Inc.
1974..
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Primary Examiner: Gupta; Yogendra N.
Attorney, Agent or Firm: Christie, Parker & Hale,
LLP
Parent Case Text
This is a continuation of application Ser. No. 08/331,144, filed
Oct. 27, 1994, now abandoned; which is a continuation of
application Ser. No. 07/746,917, filed Aug. 19, 1991, now
abandoned.
Claims
What is claimed is:
1. A rigid-rod macromonomer of the formula: ##STR21## wherein each
A.sub.1, A.sub.2, A.sub.3, and A.sub.4, on each monomer unit,
independently, is C or N; each G.sub.1, G.sub.2, G.sub.3, and
G.sub.4, on each monomer unit, independently, is H or a
solubilizing side group, provided that at least one monomer unit
has at least one solubilizing side group, wherein said solubilizing
side groups provide macromonomers with a solubility of at least
0.5% by weight in the solvent system from which they are formed,
and provided that when any of A.sub.1, A.sub.2, A.sub.3, and
A.sub.4 is N, the corresponding G.sub.1, G.sub.2, G.sub.3, or
G.sub.4 is nil, wherein said solubilizing side groups G are
selected from the group consisting of Phenyl, biphenyl, naphthyl,
phenanthryl, anthracenyl, benzyl, benzoyl, naphthoyl, phenoxy,
phenoxyphenyl, phenoxybenzoyl, alkyl, alkyl ketone, aryl, aryl
ketone, aralkyl, alkaryl, alkoxy, aryloxy alkyl ester, aryl ester,
amide, alkyl amide, dialkyl amide, aryl amide, diaryl amide, alkyl
aryl amide, amides of cyclic amines such as piperidine, piperazine
and morpholine, alkyl ether, aryl ether, alkyl sulfides, aryl
sulfides, alkyl sulfones, aryl sulfones, thioether, fluoro,
trifluoromethyl, perfluoroalkyl, and pyridyl, where alkyl is a
linear or branched hydrocarbon chain having between 1 and 30 carbon
atoms, and aryl is any single, multiple or fused ring aromatic or
heteroaromatic group having between 3 and 30 carbon atoms, and
fluorine-substituted analogs of the aforementioned G groups; E is a
reactive end group selected from the group consisting of acetals,
acetylenes, acetyls, acid anhydrides, acrylamides, acrylates,
aldehydes, alkyl aldehydes, amides, amines, anilines, aryl
aldehydes, azides, benzocyclobutenes, biphenylenes, carboxylates,
carboxylic anhydrides, cyanates, cyanides, epoxides, esters,
ethers, formyls, fulvenes, heteroaryls, hydrazines, hydroxylamines,
imides, imines, isocyanates, ketals, ketoalkyls, ketoaryls,
ketones, maleimides, nadimides, nitriles, olefins, phenols,
phosphates, phosphonates, silanes, silicates, silicones, silyl
ethers, styrenes, sulfonamides, sulfones, sulfonic acids and their
salts, sulfoxides, tetrahydropyranyl ethers, thioethers, urethanes,
vinyl ethers, and vinyls; the macromonomer has an average degree of
polymerization, DP.sub.n, greater than 6; and adjacent monomer
units are oriented head-to-head, head-to-tail, or randomly.
2. A macromonomer according to claim 1, wherein the solubilizing
side group is selected from the group consisting of alkyls, amides,
aryls, aryl sulfides, aryl sulfones, esters, ethers, thioethers,
fluoroalkyls, and ketones.
3. A macromonomer according to claim 1, wherein G.sub.1 is an
arylketone and E is an amine-derived end group.
4. A macromonomer according to claim 1, wherein G.sub.1 is an
arylketone and E is selected from the group consisting of amides,
carboxylic acids, carboxylic acid halides, carboxylic anhydrides,
and esters.
5. A macromonomer according to claim 1, wherein G.sub.1 is an
arylketone and E comprises an alcohol.
6. A macromonomer according to claim 1, wherein G.sub.1 is an
arylketone and E is selected from the group consisting of epoxide,
vinyl, and imide groups.
7. A macromonomer according to claim 1, wherein G.sub.1 is an aryl
group and E is an amine-derived end group.
8. A macromonomer according to claim 1, wherein G.sub.1 is an aryl
group and E is selected from the group consisting of amides,
carboxylic acids, carboxylic acid halides, carboxylic anhydrides,
and esters.
9. A macromonomer according to claim 1, wherein G.sub.1 is an aryl
group and E comprises an alcohol.
10. A macromonomer according to claim 1, wherein G.sub.1 is an aryl
group and E is selected from the group consisting of epoxide,
vinyl, and imide groups.
11. A macromonomer according to claim 1, wherein G.sub.1 is an aryl
ether and E is an amine-derived end group.
12. A macromonomer according to claim 1, wherein G.sub.1 is an aryl
ether and E is selected from the group consisting of amides,
carboxylic acids, carboxylic acid halides, carboxylic anhydrides,
and esters.
13. A macromonomer according to claim 1, wherein G.sub.1 is an aryl
ether and E comprises an alcohol.
14. A macromonomer according to claim 1, wherein G.sub.1 is an aryl
ether and E is selected from the group consisting of epoxide,
vinyl, and imide groups.
15. A macromonomer according to claim 1, wherein G.sub.1 is an
amide and E is an amine-derived end group.
16. A macromonomer according to claim 1, wherein G.sub.1 is an
amide and E is selected from the group consisting of amides,
carboxylic acids, carboxylic acid halides, carboxylic anhydrides,
and esters.
17. A macromonomer according to claim 1, wherein G.sub.1 is an
amide and E comprises an alcohol.
18. A macromonomer according to claim 1, wherein G.sub.1 is an
amide and E is selected from the group consisting of epoxide,
vinyl, and imide groups.
19. A rigid-rod macromonomer of the formula: ##STR22## wherein each
A.sub.1, A.sub.2, A.sub.3, and A.sub.4, on each monomer unit,
independently, is C or N; each G.sub.1, G.sub.2, G.sub.3, and
G.sub.4, on each monomer unit, independently, is selected from the
group consisting of H, solubilizing side groups, and reactive side
groups, provided that at least one monomer unit has at least one
solubilizing side group, wherein said solubilizing side groups
provide macromonomers with a solubility of at least 0.5% by weight
in the solvent system from which they are formed, and provided that
when any of A.sub.1, A.sub.2, A.sub.3, and A.sub.4 is N, the
corresponding G.sub.1, G.sub.2, G.sub.3, or G.sub.4 is nil, wherein
said solubilizing side groups G are selected from the group
consisting of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl,
benzyl, benzoyl, phenoxybenzoyl, alkyl, alkyl ketone, aryl, aryl
ketone, aralkyl, alkaryl, alkoxy, aryloxy, alkyl ester, aryl ester,
amide, alkyl amide dialkyl amide, aryl amide, diaryl amide, alkyl
aryl amide, amides of cyclic amines such as piperidine piperazine
and morpholine, alkyl ether, aryl ether, alkyl sulfides, aryl
sulfides, alkyl sulfones, aryl sulfones, thioether, fluoro,
trifluoromethyl, perfluoroalkyl, and pyridyl, where alkyl is a
linear or branched hydrocarbon chain having between 1 and 30 carbon
atoms, and aryl is any single, multiple or fused ring aromatic or
heteroaromatic group having between 3 and 30 carbon atoms, and
fluorine-substituted analogs of the aforementioned G groups; E is a
reactive end group; the macromonomer has a degree of
polymerization, DP.sub.n, greater than about 6: and adjacent
monomer units are oriented head-to-head, head-to-tail, or randomly;
wherein the reactive side groups and reactive end groups E are
independently selected from the group consisting of acetals,
acetylenes, acetyls, acid anhydrides, acrylamides, acrylates,
aldehydes, alkyl aldehydes, alkyl halides, amides, amines,
anilines, aryl aldehydes, azides, benzocyclobutenes, biphenylenes,
carboxylates, carboxylic anhydrides, cyanates, cyanides, epoxides,
esters, ethers, formyls, fulvenes, heteroaryls, hydrazines,
hydroxylamines, imides, imines, isocyanates, ketals, ketoalkyls,
ketoaryls, ketones, maleimides, nadimides, nitrites, olefins,
phenols, phosphates, phosphonates, silanes, silicates, silicones,
silyl ethers, styrenes, sulfonamides, sulfones, sulfonic acids and
their salts, sulfoxides, tetrahydropyranyl ethers, thioethers,
urethanes, vinyl ethers, and vinyls.
20. A rigid-rod macromonomer according to claim 19, wherein at
least one monomer unit has at least one reactive side group.
21. A rigid-rod macromonomer according to claim 19, wherein a
plurality of monomer units have at least one reactive side
group.
22. A rigid-rod macromonomer of the formula: ##STR23## wherein each
A.sub.1, A.sub.2, A.sub.3, and A.sub.4, on each monomer unit,
independently, is C or N; each G.sub.1, G.sub.2, G.sub.3, and
G.sub.4, on each monomer unit, independently, is H or a
solubilizing side group, provided that at least one monomer unit
has at least one solubilizing side group wherein said solubilizing
side groups provide macromonomers with solubility of at least 0.5%
by weight in the solvent system from which they were formed, and
provided that when any of A.sub.1, A.sub.2, A.sub.3, and A.sub.4 is
N, the corresponding G.sub.1, G.sub.2, G.sub.3, or G.sub.4 is nil;
E is a reactive end group; the macromonomer has an average degree
of polymerization, DP.sub.n, greater than 6; and adjacent monomer
units are oriented head-to-head, head-to-tail, or randomly; the
combinations of G.sub.1 and E selected from the group consisting of
the following:
1) G.sub.1 is an arylketone and E is an amine-derived end
group;
2) G.sub.1 is an arylketone and E is selected from the group
consisting of amides, carboxylic acids, carboxylic acid halides,
carboxylic anhydrides, and esters;
3) G.sub.1 is an arylketone and E comprises an alcohol;
4) G.sub.1 is an arylketone and E is selected from the group
consisting of epoxide, vinyl, and imide groups;
5) G.sub.1 is an aryl group and E is an amine-derived end
group;
6) G.sub.1 is an aryl group and E is selected from the group
consisting of amides, carboxylic acids, carboxylic acid halides,
carboxylic anhydrides, and esters;
7) G.sub.1 is an aryl group and E comprises an alcohol;
8) G.sub.1 is an aryl group and E is selected from the group
consisting of epoxide, vinyl, and imide groups;
9) G.sub.1 is an aryl ether and E is an amine-derived end
group;
10) G.sub.1 is an aryl ether and E is selected from the group
consisting of amides, carboxylic acids, carboxylic acid halides,
carboxylic anhydrides, and esters;
11) G.sub.1 is an aryl ether and E comprises an alcohol;
12) G.sub.1 is an aryl ether and E is selected from the group
consisting of epoxide, vinyl, and imide groups;
13) G.sub.1 is an amide and E is an amine-derived end group;
14) G.sub.1 is an amide and E is selected from the group consisting
of amides, carboxylic acids, carboxylic acid halides, carboxylic
anhydrides, and esters;
15) G.sub.1 is an amide and E comprises an alcohol; and
16) G.sub.1 is an amide and E is selected from the group consisting
of epoxide, vinyl, and imide groups.
23. A rigid-rod macromonomer of the formula: ##STR24## wherein each
A.sub.1, A.sub.2, A.sub.3, and A.sub.4, on each monomer unit,
independently, is C or N; each G.sub.1, G.sub.2, G.sub.3, and
G.sub.4, on each monomer unit, independently, is H or a
solubilizing side group, provided that at least one monomer unit
has at least one solubilizing side group, wherein said solubilizing
side groups provide macromonomers with solubility of at least 0.5%
by weight in the solvent system from which they were formed, and
provided that when any of A.sub.1, A.sub.2, A.sub.3, and A.sub.4 is
N, the corresponding G.sub.1, G.sub.2, G.sub.3, or G.sub.4 is nil,
wherein said solubilizing side groups G are selected from the group
consisting of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl,
benzyl, benzoyl, naphthoyl, phenoxy, phenoxyphenyl, phenoxybenzoyl,
alkyl, alkyl ketone, aryl, aryl ketone, aralkyl, alkaryl, alkoxy,
aryloxy, alkyl ester, aryl ester, amide, alkyl amide, dialkyl
amide, aryl amide, diaryl amide, alkyl aryl amide, amides of cyclic
amines such as piperidine, piperazine and morpholine, alkyl ether,
aryl ether, alkyl sulfides, aryl sulfides, alkyl sulfones, aryl
sulfones, thioether, fluoro, trifluoromethyl, perfluoroalkyl, and
pyridyl, where alkyl is a linear or branched hydrocarbon chain
having between 1 and 30 carbon atoms, and aryl is any single,
multiple or fused ring aromatic or heteroaromatic group having
between 3 and 30 carbon atoms, and fluorine-substituted analogs of
the aforementioned G groups; E is a reactive end group selected
from the group consisting of acetals, acetals from ethylvinylether,
acetylenes, acetyls, acid anhydrides, acids, acrylamides,
acrylates, alcohols, aldehydes, alkyl aldehydes, alkyl halides,
amides, amines, anilines, aryl aldehydes, azides,
benzocyclobutenes, biphenylenes, carboxylates, carboxylic acids and
their salts, carboxylic acid halides, carboxylic anhydrides,
cyanates, cyanides, epoxides, esters, ethers, formyls, fulvenes,
halides, heteroaryls, hydrazines, hydroxylamines, imides, imines,
isocyanates, ketals, ketoalkyls, ketoaryls, ketones, maleimides,
nadimides, nitriles, olefins, phenols, phosphates, phosphonates,
quaternary amines, silanes, silicates, silicones, silyl ethers,
styrenes, sulfonamides, sulfones, sulfonic acids and their salts,
sulfonyl halides, sulfoxides, tetrahydropyranyl ethers, thioethers,
urethanes, vinyl ethers, and vinyls; the macromonomer has a degree
of polymerization, DP.sub.n, greater than 15; and adjacent monomer
units are oriented head-to-head, head-to-tail, or randomly.
24. A macromonomer according to claim 23, wherein the solubilizing
side group is selected from the group consisting of alkyls, amides,
aryls, aryl sulfides, aryl sulfones, esters, ethers, thioethers,
fluoroalkyls, and ketones.
25. A soluble rigid-rod macromonomer of the formula: ##STR25##
wherein each A.sub.1, A.sub.2, A.sub.3, and A.sub.4, on each
monomer unit, independently, is C or N; each G.sub.1, G.sub.2,
G.sub.3, and G.sub.4, on each monomer unit, independently, is H or
a solubilizing side group, provided that at least one monomer unit
has at least one solubilizing side group, wherein said solubilizing
side groups provide macromonomers with solubility of at least 0.5%
by weight in the solvent system from which they were formed, and
provided that when any of A.sub.1, A.sub.2, A.sub.3, and A.sub.4 is
N, the corresponding G.sub.1, G.sub.2, G.sub.3, or G.sub.4 is nil,
wherein said solubilizing side groups G are selected from the group
consisting of phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl,
benzyl, benzoyl, naphthoyl, phenoxy, phenoxyphenyl, phenoxybenzoyl,
alkyl, alkyl ketone, aryl, aryl ketone, aralkyl, alkaryl, alkoxy,
aryloxy, alkyl ester, aryl ester, amide, alkyl amide, dialkyl
amide, aryl amide, diaryl amide, alkyl aryl amide, amides of cyclic
amines such as piperidine, piperazine and morpholine, alkyl ether,
aryl ether, alkyl sulfides, aryl sulfides, alkyl sulfones, aryl
sulfones, thioether, fluoro, trifluoromethyl, perfluoroalkyl, and
pyridyl, where alkyl is a linear or branched hydrocarbon chain
having between 1 and 30 carbon atoms, and aryl is any single,
multiple or fused ring aromatic or heteroaromatic group having
between 3 and 30 carbon atoms, and fluorine-substituted analogs of
the aforementioned G groups; E is a reactive end group selected
from the group consisting of alkyl halides, sulfonyl halides, and
carboxylic acid halides; the macromonomer has an average degree of
polymerization, DP.sub.n, greater than 6; and adjacent monomer
units are oriented head-to-head, head-to-tail, or randomly.
26. A macromonomer according to claim 25, wherein the solubilizing
side group is selected from the group consisting of alkyls, amides,
aryls, aryl sulfides, aryl sulfones, esters, ethers, thioethers,
fluoroalkyls, aryl ketones and alkyl ketones.
27. A macromonomer according to claim 26, wherein G.sub.1 is an
aryl ketone.
28. A macromonomer according to claim 26, wherein G.sub.1 is
benzoyl.
29. A macromonomer according to claim 25, wherein the reactive end
group E is a carboxylic acid halide.
30. A macromonomer according to claim 25, wherein the reactive end
group E is an alkyl halide.
31. A macromonomer according to claim 25, wherein the reactive end
group E is a sulfonyl halide.
Description
FIELD OF THE INVENTION
This invention relates to soluble macromonomers having rigid-rod
backbones, pendant, flexible, solubilizing organic groups attached
to the backbone, and reactive end groups at the ends of the
macromonomer chains. They can be chemically incorporated into other
polymer and monomer systems to yield strengthened, stiffened
polymer compositions.
BACKGROUND OF THE INVENTION
It is well known that the stiffness and strength of a polymer are
related to the flexibility of the polymer chain on the molecular
level. Thus, if the chemical structure of the main chain restricts
chain coiling and flexing, the resulting polymer will be stiff and
strong. An example of a stiff polymer is
poly-1,4-pheny-lene-1,4-terephthalamide (PPTA). While PPTA can coil
in solution, the amide linkages and para-phenylene groups favor an
extended chain conformation. Fibers can be prepared in which the
chains are essentially all extended into rod-like conformations,
and these fibers are extraordinarily strong and stiff.
Unfortunately, PPTA is difficult to process (except for fiber
spinning) and cannot be molded or extruded. In general, the more
rigid the polymer main chain the more difficult it is to prepare
and process.
Some applications require strong, stiff materials that can be
easily processed by molding or extrusion. A widely used approach to
obtain such stiff materials is to add fillers such as carbon or
silica, or to incorporate fibers, such as glass and carbon fibers,
into a relatively flexible polymer, thereby forming a stiff, strong
composite material. The most widely utilized, high-performance
fiber-polymer composites are composed of oriented carbon (graphite)
fibers embedded in a suitable polymer matrix.
The improvements in strength and stiffness of composites are
related to the aspect ratio of the filler or fiber, i.e., the
length to diameter ratio of the smallest diameter cylinder that
will enclose the filler or fiber. To contribute reasonable strength
and stiffness to the composite, the fibers must have an aspect
ratio of at least about 25, and preferably at least 100. Continuous
fibers have the highest aspect ratio and yield the best mechanical
properties but are costly to process. Low aspect ratio materials,
such as chopped fibers and fillers, give limited improvement in
mechanical properties but are easy and inexpensive to process. The
success of composites is demonstrated by their wide use as
structural materials.
There are several drawbacks associated with composite materials.
Composites are often more costly than the unreinforced polymer.
This is because of the expense of the fiber component and the
additional labor needed to prepare the composite. Composites are
difficult or impossible to repair and, in general, cannot be
recycled. Many composites also have undesirable failure
characteristics, failing unpredictably and catastrophically.
Molecular composites (composed of polymeric materials only) offer
the prospect of high performance, lower cost and easier
processability than conventional fiber-polymer composites. In
addition, molecular composites generally can be recycled and
repaired. Because molecular composites contain no fibers, they can
be fabricated much more easily than fiber-polymer compositions,
which contain macroscopic fibers.
Molecular composites are materials composed of a rigid-rod polymer
embedded in a flexible polymer matrix. The rigid-rod polymer in a
molecular composite can be thought of as the microscopic equivalent
of the fiber in a fiber-polymer composite. The flexible polymer
component of a molecular composite serves to disperse the rigid-rod
polymer, preventing bundling of the rigid-rod molecules. As in
conventional fiber/resin composites, the flexible polymer in a
molecular composite helps to distribute stress along the rigid-rod
molecules via elastic deformation of the flexible polymer. Thus,
the second, or matrix-resin, polymer must be sufficiently flexible
to effectively surround the rigid-rod molecules while still being
able to stretch upon stress. The flexible and rigid-rod polymers
can also interact strongly via Van der Waals, hydrogen bonding, or
ionic interactions. The advantages of molecular composites have
been demonstrated by W. F. Hwang, D. R. Wiff, C. L. Brenner and T.
E. Helminiak, Journal of Macromolecular Science Phys, B22, 231-257
(1983).
Molecular composites are simple mixtures or blends of a rigid-rod
polymer with a flexible polymer. As is known in the art, most
polymers do not mix with other polymers, and attempts at blends
lead to macroscopic phase separation. This is also true of
rigid-rod polymer/flexible polymer blends. Metastable blends may be
prepared by rapid coagulation from solution. However, metastable
blends will phase separate on heating, ruling out further thermal
processing, such as molding or melt spinning. The problem of
macroscopic phase separation is reported by H. H. Chuah, T. Kyu and
T. E. Helminiak, Polymer, 28, 2130-2133 (1987). Macroscopic phase
separation is a major limitation of molecular composites.
Rigid-rod polymers produced in the past are, in general, highly
insoluble (except in the special case of polymers with basic
groups, which may be dissolved in strong acids or in organic
solvents with the aid of Lewis acids) and infusible. Preparation
and processing of such polymers is, accordingly, difficult. A
notable exception is found in U.S. Pat. application Ser. No.
07/397,732, filed Aug. 23, 1989 now U.S. Pat. No. 5,227,457
(assigned to the assignee of the present invention), which is
incorporated herein by this reference. The rigid-rod polymers
described in the above-referenced application have a rigid-rod
backbone comprising a chain length of at least 25 organic monomer
units joined together by covalent bonds wherein at least about 95%
of the bonds are substantially parallel; and solubilizing organic
groups attached to at least 1% of the monomer units. The polymers
are prepared in a solvent system that is a solvent for both the
monomer starting materials and the rigid-rod polymer product. The
preferred monomer units include: paraphenyl, parabiphenyl,
paraterphenyl, 2,6-quinoline, 2,6-quinazoline,
paraphenylene-2-benzobisthiazole, paraphenylene-2-benzobisoxazole,
paraphenylene-2-benzobisimidazole, paraphenylene-1-pyromellitimide,
2,6-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,4-anthracenyl,
1,10-anthracenyl, 1,5-anthracenyl, 2,6-anthracenyl,
9,10-anthracenyl, and 2,5-pyridinyl.
The rigid-rod polymers described above can be used as
self-reinforced engineering plastics and exhibit physical
properties and cost-effectiveness superior to that exhibited by
many conventional fiber-containing composites.
It would be quite useful if rigid-rod polymers could be
incorporated into conventional flexible polymers, especially large
volume commodity polymers. The value of a flexible polymer would be
increased significantly if its mechanical properties could be
enhanced by addition of rigid-rod polymers. Such molecular
composites could displace more expensive engineering resins and
specialty polymers and conventional composites as well. To date,
practical molecular composites have not been demonstrated. This is
chiefly due to deficiencies in currently available rigid-rod
polymers, namely limited solubility and fusibility, and unfavorable
chemical and physical interactions between the rigid-rod and
flexible polymer component.
There is a need in the art for a rigid-rod polymer that can be
chemically incorporated into flexible polymers and polymer systems,
during or subsequent to polymerization, to thereby add strength
and/or stiffness to the resulting polymers. Chemical rather than
physical incorporation is desirable to inhibit phase separation
during the processing and use of the polymer and to increase the
resulting polymer's solvent resistance. The mechanical behavior of
polymer systems which contain chemically incorporated rigid-rod
moieties can be different and superior to physical blends of, for
example, rigid-rod polymers with flexible polymers.
SUMMARY OF THE INVENTION
It has now been found that, for any given polymer, improvements in
stiffness and strength can be obtained by preparing a copolymer,
thermoset resin, or the like, which incorporates rigid segments and
the more flexible segments of the original polymer. These rigid
segments act in a manner conceptually similar to the way stiff
fibers act to reinforce composites; however, in the present
invention no macroscopic fibers are present.
In the present invention, the problem of macroscopic phase
separation, found in molecular composites, is avoided by the use of
rigid-rod macromonomers having reactive end groups. In one
embodiment of the present invention, the rigid-rod macromonomers
are made to react with flexible polymers, via reactive end groups,
to form covalent bonds between the rigid-rod macromonomer and the
flexible polymer, thereby preventing macroscopic phase
separation.
In a second embodiment, macroscopic phase separation is prevented
by forming the flexible polymer in the presence of the
macromonomer. The reactive end groups of the macromonomer react
with monomers during polymerization of the flexible polymer,
forming covalent bonds between the macromonomer and flexible
polymer.
In a third embodiment, the rigid-rod macromonomer is modified, by
way of chemical transformation of its reactive end groups, such
that the end groups are made compatible with the flexible polymers.
Compatibilizers include groups which will interact with the
flexible polymer ionically, by hydrogen bonding, or by van der
Waals interactions. Compatibilizers may be polymeric, or
oligomeric. For example, a rigid-rod macromonomer may be made to
react, via its reactive end groups, with caprolactam to form short
polycaprolactam chains at either end, the resulting
polycaprolactam-modified macromonomer being compatible with
polycaprolactam.
In a fourth embodiment, the rigid-rod monomers are used alone to
form thermosetting resins. In this case, the reactive end groups
provide some degree of processability and will react under the
appropriate conditions, e.g., heat, irradiation, exposure to air,
etc., to form crosslinks and effect curing.
Other methods of incorporating the rigid-rod macromonomers of the
present invention into materials are contemplated and depend on the
chemistry and properties of the material to be modified.
It should be understood that while macroscopic phase separation is
prevented, there may be varying degrees of microscopic phase
separation. Microscopic phase separation results in the formation
of phases having size on the order of the dimensions of the polymer
chain. Microphase separation may be conducive to significant
improvements in mechanical or other properties desired from
incorporation of rigid-rod macromonomers.
The macromonomers of the present invention have the structure (1):
##STR2## where each G.sub.1, G.sub.2, G.sub.3, and G.sub.4, on each
monomer unit, independently, is a solubilizing side group or
hydrogen, E is a functional ("reactive") end group, and the number
average degree of polymerization, DP.sub.n, is greater than about
6. If DP.sub.n is less than about 7 or 8, the rigidity and
stiffness of the resulting macromonomer-reinforced polymer is only
slightly increased. In some applications, however, macromonomers
prepared in accordance with the present invention having a DP.sub.n
as low as 4 may be useful, e.g., for decreasing the thermal
expansion coefficient of a flexible polymer, such as a polyimide or
polyamide. Preferably, DP.sub.n is between 10 and 500. G will be
used to mean a general solubilizing group and G.sub.1, G.sub.2,
G.sub.3, and G.sub.4 specific solubilizing groups.
The structures presented here show only a single monomer unit and
do not imply regular head-to-tail arrangement of monomer units
along the chain. Monomer units may have random orientation, or may
be alternating head-to-head, tail-to-tail, or regular head-to-tail,
or have other arrangements, depending on the conditions of the
polymerization and reactivity of monomers.
The macromonomers of the present invention may also contain
heteroatoms in the main chain. Heteroaromatic rigid-rod
macromonomers have structure (2), where A.sub.1, A.sub.2, A.sub.3,
and A.sub.4 on each monomer unit, independently, may be carbon or
nitrogen and G and E are as defined above, except that where an A
is nitrogen, the corresponding G is nil. ##STR3##
Additionally, other rigid-rod monomer units can be incorporated
into the macromonomers prepared in accordance with the present
invention. Thus a rigid-rod macromonomer having monomer units of
the type shown in structures (1) and/or (2) and benzobisthiazole
monomer units ##STR4## can be used in the same way as (1) and (2).
Likewise, rigid-rod pyromellitimide, benzobisoxazole,
benzobisimidazole and other rigid-rod monomer units may be
substituted for some of the phenylene units without loss of
function. The benzobisimidazole, thiazole and oxazole units can
have either cis or trans configuration.
The rigid-rod macromonomers of the present invention may be further
polymerized or cured by virtue of their reactive end groups.
Depending on the nature of the end groups and cure conditions,
either linear, branched or network structures result.
The macromonomers of the present invention may be used to form
thermosets, either alone or in combination with other thermosetting
polymers. The macromonomers may also be used with thermoplastics,
e.g., by forming a copolymer.
DETAILED DESCRIPTION OF THE INVENTION
As discussed above, the strength and stiffness of a polymer are
related to the flexibility of the polymer chain on a molecular
level. It has now been found that for any given polymer,
improvements in stiffness and strength can be obtained by preparing
a copolymer having rigid segments as well as the more flexible
segments of the original polymer. These rigid segments act in a
manner conceptually similar to the way stiff fibers act to
reinforce composites, however, in the present invention no
macroscopic fibers are present. The rigid segments are provided by
incorporating rigid-rod macromonomers having structures (1) and/or
(2) during or subsequent to polymerization of the flexible polymer.
Several approaches are provided by the present invention.
Macromonomers having structure (1) are solubilized
polyparaphenylenes having reactive functional end groups.
Macromonomers having structure (2) are aza derivatives of
polyparaphenylenes having reactive end groups. In each case,
G.sub.1 through G.sub.4 are solubilizing side groups or hydrogen, E
is a functional end group, and the number average degree of
polymerization, DP.sub.n is greater than about 6, preferably
between 10 and 500.
As used herein, the term "endcapper" shall mean any reagent which
serves to terminate growth of one or both ends of the macromonomer
being formed, thus preventing further extension of the rigid-rod
macromonomer backbone via the ongoing macromonomer-forming
reaction, and which results in a "reactive end group", E, being
chemically incorporated into that end of the rigid-rod macromonomer
molecule.
The terms "reactive end group," "functional end group," and the
like, are defined to mean any chemical moiety incorporated into an
end of a rigid-rod macromonomer molecule, which chemical moiety can
be used in a subsequent reaction to effect one or more of the
following reactions:
a) Reaction with a flexible polymer resulting in formation of one
or more covalent bonds between the macromonomer and the flexible
polymer;
b) Reaction with monomers, either before or during a reaction in
which such monomers are polymerized to give a flexible polymer,
resulting in formation of one or more covalent bonds between the
macromonomer and the resulting flexible polymer;
c) Reaction with an oligomer or other small molecular species,
resulting in increased compatibility of the rigid-rod macromonomer
with flexible polymers in blends, mixtures, composites, copolymers,
composites, alloys and the like; and
d) Polar, ionic, or covalent interaction with an inorganic matrix,
resulting in a modified ceramic or an inorganic glass or glass-like
material.
Reactive groups may be transformed by further chemical reaction
including, without limitation, oxidation, reduction, deprotonation,
halogenation, Schiff base formation, hydrolysis, electrophilic or
nucleophilic substitution, and the like, to yield new reactive
groups.
One skilled in the art will recognize that it sometimes will be
desirable to incorporate such endcapper reactive groups in a
protected form in order to ensure that the reactive group does not
poison or otherwise participate in or interfere with the
macromonomer-forming reaction, e.g., an amine can be incorporated
as an amide, a carboxylic acid can be incorporated as an ester, and
an alcohol can be incorporated as an ester or as an ether. Once
formation of the macromonomer has been completed the protected
reactive end group can then be deprotected, e.g., an amide or an
ester can be hydrolyzed to produce an amine and an alcohol,
respectively.
Nonlimiting examples of reactive end groups, E, include acetals,
acetals from ethylvinylether, acetylenes, acetyls, acid anhydrides,
acids, acrylamides, acrylates, alcohols, aldehydes, alkanols, alkyl
aldehydes, alkyl halides, amides, amines, anilines, aryl aldehydes,
azides, benzocyclobutenes, biphenylenes, carboxylates, carboxylic
acids and their salts, carboxylic acid halides, carboxylic
anhydrides, cyanates, cyanides, epoxides, esters, ethers, formyls,
fulvenes, halides, heteroaryls, hydrazines, hydroxylamines, imides,
imines, isocyanates, ketals, ketoalkyls, ketoaryls, ketones,
maleimides, nitriles olefins, phenols, phosphates, phosphonates,
quaternary amines, silanes, silicates, silicones, silyl ethers,
styrenes, sulfonamides, sulfones, sulfonic acids and their salts,
sulfonyl halides, sulfoxides, tetrahydropyranyl ethers, thioethers,
urethanes, vinyl ethers, vinyls, and the like. In some cases, the
functional end groups are capable of reacting with each other.
One skilled in the art will recognize that reactive groups can be
prepared from "non-reactive" groups and "less reactive" groups. For
example, some applications make it desirable to incorporate a rigid
rod polymer having tolyl end groups into a flexible polyester. The
tolyl group is unreactive toward polyesters or polyester monomers,
however, the tolyl group can be oxidized to a reactive
carboxyphenyl group which then can react with polyesters by
trans-esterification, or with polyester monomers to form polyesters
containing the rigid rod macromonomer. Similarly, a relatively
non-reactive acetyl group can be modified by formation of a
Schiff's base with 4-aminophenol, to give a macromonomer having
phenolic end groups, useful for reinforcing thermoset resins such
as epoxies and phenolics. Other examples will be apparent to those
skilled in the art.
The term "solubilizing side group" as used herein means a chemical
moiety which, when attached to the backbone of the macromonomer,
improves the solubility of the macromonomer in an appropriate
solvent system. For the purposes of the present invention, the term
"soluble" will mean that a solution can be prepared containing
greater than 0.5% by weight of the macromonomer or greater than
about 0.5% of the monomer(s) being used to form the
macromonomer.
It is understood that various factors must be considered in
choosing a solubilizing group for a particular polymer and solvent,
and that, all else being the same, a larger or higher molecular
weight solubilizing group will induce a higher degree of
solubility. Conversely, for smaller solubilizing groups, matching
the properties of the solvent and solubilizing groups is more
critical, and it may be necessary to have, in addition, other
favorable interactions inherent in the structure of the polymer to
aid in solubilization.
In some embodiments of the invention, some of the side groups G
will also be "reactive" functional groups, in the same sense that
the end groups E are reactive.
The number average degree of polymerization, DP.sub.n is defined
by:
DP.sub.n =(number of monomer molecules present initially)/ (number
of polymer or oligomer chains in the system).
The number average molecular weight, M.sub.n is defined by:
where M.sub.o is the weight of one monomer unit in the chain. We
will use a convention where the end groups are not counted in
figuring the DP.sub.n. The end groups make only small contribution
to the molecular weight and are not included in the definition.
As described below in greater detail, the rigid-rod macromonomers
of the present invention are formed by reacting a macromonomer with
an "endcapper" or endcapping moiety. The endcapper provides the
functional end group E, directly or by chemical transformation
(including, e.g., deprotection) into E.
For an ideal condensation polymerization, DP.sub.n may be
calculated given the initial amounts of monomer and endcapper
described below by:
In practice, this is usually an upper limit due to adventitious
endcapping reactions which lower the molecular weight of the
macromonomer. When adventitious endcappers (impurities) are
present, DP.sub.n =2.times.mols monomer .div.[(mols of
endcapper)+(mols of adventitious endcapping impurities)]. If the
amount of adventitious endcapper is small, then the observed
DP.sub.n will be close to that which is calculated neglecting
impurities.
Side reactions will also limit molecular weight of the
macromonomers. Side reactions may be accounted for in calculation
of DP.sub.n by including a term for the extent of reaction, as
described below in the discussion following General Procedures
I-III.
The number average degree of polymerization DP.sub.n is indicated
in structural formulae, as in structure (1), by "n".
Compounds having structure (1) or (2) are rigid-rod macromonomers
having reactive end groups. Such macromonomers are rigid or stiff
on both the microscopic and macroscopic level. These macromonomers
can be incorporated into other polymers via the two reactive end
groups, E, and will impart stiffness and strength to the resultant
polymers. Compounds of this type are sometimes called telechelic
polymers or telechelic oligomers. The distinction between oligomers
and polymers is that the
properties of an oligomer change measurably on changing the degree
of polymerization by one, while for a polymer adding an additional
monomer unit has little effect on properties. Since the range of
DP.sub.n (>6) considered here covers both oligomers and
polymers, and since this technical distinction is not of great
importance to the applications of these compounds, we will use the
term macromonomer to imply the entire range from oligomers to
polymers.
In macromonomers having structure (2), if only one of the A's is
nitrogen, for example if A.sub.4 is N, substituted polypyridines of
structure (3) result: ##STR5##
If only A.sub.1 and A.sub.2 are N, the monomer unit is a
pyridazine; if only A.sub.1 and A.sub.3 are N, the monomer unit is
a pyrazine, if only A.sub.1 and A.sub.4 are N, the monomer unit is
a pyrimidine. If three A's are N, the monomer unit is a triazine.
Other heterocyclic monomer units are included if some of the G's
are bridging, for example, if G.sub.1 and G.sub.2 are --CHCHCHCH--,
and A.sub.3 is N, the monomer unit is an isoquinoline.
Macromonomers having the structure (2) include compounds of the
structure (1) as a subset.
It is possible to have rigid-rod macromonomers in accordance with
the present invention comprising several types of monomer units,
each with a different set of A's and G's, i.e., each A.sub.1,
A.sub.2, A.sub.3 and A.sub.4 on each monomer unit, independently is
C or N, and each G.sub.1, G.sub.2, G.sub.3, and G.sub.4 on each
monomer unit, independently is H or a solubilizing side group. In
other words, adjacent monomer units need not be identical.
Macromonomers comprised of different monomers are copolymer-type
macromonomers and are usually prepared using more than one
monomer.
As stated above, the number and type of side groups necessary to
impart solubility will depend on the solvent, n and the nature of
E. If n is small, only a few side chains will be needed for
solubility. That is, only some of the monomer units in each chain
may be substituted; the rest are unsubstituted, i.e., the G's are
all H. Where n is very small and E aids solubility, all the G's may
be H. Where n is large, solubility may be maintained by using more
non-H G's per chain or by using G's with higher molecular weight.
In many cases, the macromonomer will have exactly one non-hydrogen
G per monomer unit, i.e. G.sub.1 =solubilizing group, G.sub.2
.dbd.G.sub.3 .dbd.G.sub.4 .dbd.H. Structures (1) and (2) are meant
to imply both homopolymers and copolymers where not all monomer
units have the same set of G's.
The macromonomers of the present invention may interact differently
with different classes of flexible polymers, for example, addition
polymers and condensation polymers. A nonlimiting list of flexible
polymers that can incorporate the macromonomers of the present
invention includes polyacetals, polyamides, polyimides, polyesters,
polycarbonates, polyamide-imides, polyamide-esters, polyamide
ethers, polycarbonate-esters, polyamide-ethers, polyacrylates;
elastomers such as polybutadiene, copolymers of butadiene with one
or more other monomers, butadiene-acrylonitrile rubber,
styrene-butadiene rubber, polyisoprene, copolymers of isoprene with
one or more other monomers, polyphosphazenes, natural rubber,
blends of natural and synthetic rubber, polydimethylsiloxane,
copolymers containing the diphenylsiloxane unit;
polyalkylmethacrylates, polyethylene, polypropylene, polystyrene,
polyvinylacetate; polyvinylalcohol, and polyvinylchloride.
Reinforcing Condensation Polymers
Rigid segments may be introduced into a wide variety of
condensation polymers through the use of the rigid-rod
macromonomers of the present invention. In one embodiment, the
macromonomer is added during the polymer forming reacting
(polymerization) of the polymer to be stiffened. The polymer to be
stiffened and/or strengthened will be referred to as the flexible
polymer, regardless of its absolute stiffness. In one embodiment,
in addition to being rigid, the macromonomer will dissolve in the
flexible polymer polymerization dope and have functionality
enabling it to take part in the polymerization reaction. In another
embodiment, the initially formed flexible condensation polymer is
isolated, and a solvent is selected for both the macromonomer and
the flexible polymer. The flexible polymer and macromonomer are
redissolved, and the macromonomer reacts with the originally formed
flexible polymer. Macromonomers may also be dissolved in the melt
of the flexible polymer, where reaction of the end groups may then
occur.
Several types of condensation polymers may be distinguished.
Condensation polymers may include a single monomer, usually
referred to as an A-B monomer: ##STR6##
Alternatively, two complementary difunctional monomers, usually
referred to as A--A and B--B may be condensed: ##STR7##
Where the rigid-rod macromonomers are used in a condensation
polymerization, they may be considered A--A (or B--B) type
monomers. That is, the two reactive end groups E can be considered
to be the A--A (or B--B) type end groups typically described in
condensation polymerization systems. A--A, B--B, and A--B type
monomers are described in U.S. Pat. No. 4,000,187 to Stille,
incorporated herein by this reference. For purposes of the present
invention, the designation of particular monomers as being "A--A"
or "B--B" is arbitrary, so long as A and B are complementary
functionalities. Thus A--A can represent a diamine, e.g., and B--B
a diacid, and vice versa. If more than one type of macromonomer is
used they may be conveniently distinguished by denoting them by
"AMA", "A'MA'", "BMB", "B'MB'", and so forth.
Nonlimiting examples of A--A and B--B type monomers include
diamine-type monomers such as p-phenylenediamine,
m-phenylenediamine, oxydianiline, methylenedianiline,
tetramethylenediamine, hexamethylenediamine; diol-type monomers
such as resorcinol and hexanediol; bisaminoketones, bisthiols;
diacid-type monomers such as adipic acid, adipoyl chloride, esters
of adipic acid, terephthalic acid, terephthaloyl chloride, esters
of terephthalic acid; bisketomethylenes, bis(activated halides)
such as chlorophenyl sulfone, and the like.
Nonlimiting examples of A--B type monomers include amino acids,
amino acid esters, activated halides such as
4-fluoro-4'-hydroxybenzophenone, lactams (e.g., caprolactam),
lactones, and the like.
Several types of reinforced polymers and copolymers are possible
with rigid macromonomers. Let AMA (or BMB) represent a rigid
macromonomer. In the simplest case AMA is condensed with a B--B
monomer: ##STR8## The resulting copolymer will incorporate rigid
AMA macromonomer blocks separated by single B--B type monomer
units.
A copolymer also can be formed using AMA macromonomers in
conjunction with a second A--A monomer having similar end
functionality, and a B--B monomer: ##STR9## where the symbol "/"
indicates a random copolymer. The relative amount of rigid segments
is determined by the ratio of x to y, that is by the ratio of A--A
monomer to AMA macromonomer used. As is known in the art, the
degree of polymerization, indicated by n, may be controlled by
controlling the monomer balance, that is the ratio of B--B monomer
to the total of A--A and AMA monomers, where x+y=z is perfect
balance and gives highest n.
Rigid macromonomers AMA when used with A--B monomers result in
tri-block copolymers when the molar amount of A--B monomer is large
relative to AMA: ##STR10## In general the macromonomer will form
the center block with AB blocks at the ends. If A--B is not in
molar excess, mixtures of di and tri blocks, e.g., may result.
More complex mixtures of rigid macromonomers with A--A, B--B and
A--B monomers are also possible. Order of addition and control of
monomer imbalance can be used to create complex block copolymers.
Any set of A--A, B--B and A--B monomers which will co-condense with
an AMA (or BMB) type macromonomer will be called complementary
monomers. For example, terephthalic acid and ethylene glycol are
complementary monomers that will condense with the AMA-type
macromonomers of the present invention. Similarly, a co-polyester
can be formed by condensing AMA-type macromonomers having structure
(1) or (2) with one or more complementary monomers such as
biscarboxylic acids, biscarboxylic acid halides, biscarboxylic acid
esters, bisdiols, hydroxycarboxylic acids, lactones, and the
like.
Two variables which may be used to control the properties of the
copolymers having macromonomers incorporated therein are: the
average length of the rigid segments, L.sub.r, which is
proportional to DP.sub.n, and the weight fraction of rigid segments
in the copolymer, W.sub.r.
If A--B and/or A--A type monomers are present along with AMA and
B--B type monomers, W.sub.r is lowered. The molecular weight ratio
can also be changed by changing the macromonomer M.
Reinforcing Thermoset Resins
The rigid-rod macromonomers of the present invention may also be
used to form thermoset resins, either alone or in conjunction with
existing thermoset formulas to impart strength, stiffness, and/or a
lower coefficient of thermal expansion. Thermosets are often formed
in stages, where monomers are allowed to react to a limited extent
to give a processable resin, which is cured in a second stage,
often by heat treatment. Thermosets are typically crosslinked, and
the stages are defined by the degree of crosslinking. Aside from
the insoluble, infusible nature of the resulting cured thermoset,
the chemistry is similar to condensation polymers. Diols, polyols,
diamines and polyamines are commonly used thermoset precursors that
will react with the macromonomers of the present invention.
Rigid-rod polymers heretofore have not been used in thermosets,
primarily because it is commonly thought that rigid-rod polymers
are not soluble in resin systems, including solutions of resins or
pre-polymers used to prepare thermoset resins. The rigid-rod
macromonomers of this invention, however, are soluble in common
solvents, and can be made compatible with various resin systems by
proper choice of side groups, G. The end groups E also should be
compatible with the cure chemistry of the thermoset.
Typically, but not necessarily, E will be chosen to match the
reactive groups in the thermoset. For example, E should be an epoxy
group or an amino group for use with an epoxy resin, or a phenol
group for use with phenolic resins. It is also usually desirable
for the cure temperatures of the end groups E and the thermoset to
be similar. Nonlimiting examples of thermoset systems which can
incorporate the rigid-rod macromonomers of the present invention
are: allyl resins, benzophenonetetracarboxylic acid or its
anhydride, bisacetylene resins, bisbenzocyclobutene resins,,
bisbiphenylene resins, bisphenoltetracarboxylic acid or its
anhydride, diepoxides, epoxy resins, formaldehyde and
paraformaldehyde-based resins, furan resins, phenolic resins,
polyepoxides, pyromellitic acid or its anhydride, trioxanes,
phenol-formaldehyde resins, nrovolac resins, resole resins,
resorcinol-formaldehyde resins, silicone resins, urethanes,
melamine resins, isocyanate resins, resins based on cyanuric acid
and cyanuric chloride, polyamic acids, polyamide resins,
crosslinked polyamides and polyesters, unsaturated polyester
resins, urea resins, vinyl ester resins, and natural resins, gums,
lacquers and varnishes.
The rigid-rod macromonomers of the present invention may also be
used alone to form thermosetting resins. In this case, the side
groups G are not needed for solubility in,, or compatibility with,
other resins, polymers or monomers, but impart some degree of
thermoformability. In general, rigid-rod macromonomers with smaller
n will have lower glass transition temperatures and melting
temperatures, and will be more readily heat processed. As is known
in the art it is necessary to adjust the melting temperature and
cure temperature so that the polymer system does not cure before it
is thermoformed, and so that unreasonably high temperatures are not
needed for curing.
When used as a thermoset, the rigid-rod macromonomer must have
sufficient flow properties to be shaped or processed, typically at
elevated temperatures. Thus, the side groups G and the DP.sub.n are
chosen to allow some degree of thermoformability. In general,
larger and more flexible G's increase processability, as does lower
DP.sub.n. On the other hand, smaller G's and larger DP.sub.n 's
enhance stiffness and strength, so that optimum sizes for DP.sub.n
and G can be found. Different processing methods will have
different requirements; for example, sintering does not require
complete melting, whereas injection molding requires low viscosity
melts. The reactive end groups E of a rigid-rod macromonomer for
use as a thermoset should have a cure temperature consistent with
the required processing temperature. If the cure temperature is too
low, the material will cure before processing can be completed. If
the cure temperature is too high, the material may not fully cure
or the flow properties at the curing temperature may be
undesirable. In an exemplary and nonlimiting embodiment of the
invention, cure is effected by using a curing agent such as a
catalyst or low molecular weight crosslinking agent.
Non-limiting examples of reactive end groups with good cure
temperatures are maleimides, nadimides, and acetylenes.
Reinforcing Addition Polymers
The rigid-rod macromonomers of the present invention also find use
as pre- and post-polymerization additives. As post-polymerization
additives, rigid-rod macromonomers may be used in compounding,
blending, alloying, or otherwise mixing with preformed polymers,
preformed blends, alloys, or mixtures of polymers. In these cases
the side groups and end groups help make the macromonomer
compatible with the polymer to be reinforced. Such compounding,
blending, alloying etc. may be done by solution methods, melt
processing, milling, calendaring, grinding or other physical or
mechanical methods, or by a combination of such methods. Chemical
reaction of the end groups E of the macromonomer with the polymer
into which the macromonomer is being incorporated may take place
during such processes or E may simply make the rigid segment M
compatible with the proformed polymer, for example via non-covalent
interactions, including hydrogen bonding, ionic bonding and van der
Waals forces. Mechanical heating or shearing can initiate such
chemical processes which will effect the final composition.
For many addition polymers, where it is not convenient to introduce
the macromonomer during polymerization, the rigid-rod macromonomer
may be introduced by the above methods in post-polymerization
processes. Nonlimiting examples of such polymers include,
polyethylene, polypropylene, polyvinylchloride, polystyrene,
polyacrylonitrile, polyacrylates, ABS, SBR, and other homopolymers,
copolymers, blends, alloys etc. The above methods may also be used
with condensation polymers.
As pre-polymerization additives, the macromonomers of the present
invention are added along with other monomers to be polymerized to
yield the final polymer.
Optionally, conventional fillers such as carbon black, silica,
talc, powders, chopped or continuous fibers, or other macroscopic
reinforcing agents as are known in the art can be added to the
polymer systems which incorporate the rigid-rod macromonomers of
the present invention. In embodiments of the invention in which
macroscopic reinforcing agents are added, the macromonomers of the
present invention add additional strength, stiffness, creep
resistance, fire resistance, toughness and/or other properties to
what would otherwise be conventional composites and resins and also
serve to decrease the amount of filler used in a conventional
composite or resin.
The rigid-rod macromonomers of the present invention may be used to
enhance the properties of all types of natural and synthetic
polymers, including but not limited to, addition polymers,
condensation polymers, ring opening polymers, thermosets,
thermoplastics, elastomers, rubbers, silicones, silicone rubbers,
latexes, gums, varnishes, and cellulose derived polymers.
When used with rubbers and elastomers having a polymer network the
rigid rod macromonomers act to modify such properties as strength,
abrasion resistance, resilience, wear resistance, creep, and the
like, and may be used to replace or eliminate the use of
fillers.
The reinforced polymers of the present invention may be used to
fabricate films, fibers, and molded parts having improved
properties, especially improved mechanical properties, relative to
the same material without reinforcement by rigid-rod macromonomers.
Other non-limiting examples of applications of the reinforced
polymers of the present invention include adhesives, elastomers,
coatings, membranes, plastic sheet, and sheet molding
compounds.
Preparation of Macromonomers Having Functional End Groups
In order to introduce rigid segments into a wide variety of
polymers a rigid-rod type macromonomer is first prepared. The
poly-1,4-phenylene structure (1) and aza derivatives (structure
(2)) offer a stiff, strong, thermally stable, and chemically inert
backbone, of potentially low cost.
Several methods may be used to prepare poly-para-phenylenes and aza
analogs. The simplest rely on reductive condensation of
1,4-dihaloaromatics, either by way of a Grignard reagent, or
directly in the presence of a reducing agent such as zinc metal. A
catalyst, such as bis(triphenylphosphine) nickel (II) chloride or
1,4-dichloro-2-butene is used. Para-bromoaryl boronic acids may be
coupled using palladium based catalysts. Polyphenylenes have also
been prepared by methods which do not give exclusive para linkage,
such as Diels-Alder condensation of bis-acetylenes and bis-pyrones,
polymerization of 1,3-cyclohexadiene followed by aromatization and
oxidative polymerization of benzene.
The rigid-rod macromonomers of the present invention may be made by
these and other methods, keeping in mind the special requirements
of side groups and end groups. The catalytic reductive coupling of
1,4-dihaloaryls is preferred, (and more preferably, reductive
coupling of 1,4-dichloroaryls) because of its simplicity and wider
tolerance of functional groups. The special nature of the rigid-rod
macromonomers of the present invention must be taken into account
in order to successfully prepare these macromonomers.
The synthesis of even short rigid-rod molecules is made difficult
by their low solubility. For example, poly-1,4-phenylene (structure
(1), where G.sub.1 through G.sub.4 and E are each hydrogen)
compounds with n greater than about 8 are essentially insoluble in
all solvents, and are infusible. Solubility is achieved in the
present invention by appropriate choice of solubilizing groups G,
bearing in mind the solvent systems to be employed. For example,
for polar aprotic solvents, such as dimethylformamide or
N-methylpyrrolidone, polar aprotic side groups such as amides and
ketones are appropriate. For protic solvents, e.g. water, acids or
alcohols, ionizable side groups, e.g. pyridyl or sulfonate, might
be considered.
The solubilizing substituent may also act to twist the main chain
phenylene units out of planarity (although the main chain remains
straight and not coiled). Phenylene pairs with substituents at the
2,2' positions will be twisted out of planarity by steric
repulsion. Since planar phenylene chains pack more efficiently, a
twisted chain will be more soluble. One means of solubilizing
rigid-rod molecules is to provide adjacent phenylene pairs with
substituents ortho with respect to the other phenylene of the pair.
Even occasional 2,2' side groups will disrupt packing and enhance
solubility. Another means of improving solubility is to decrease
the order (increase the entropy) of the side groups, for example by
a random copolymer with two or more different types of
substituents. Other mechanisms of increasing solubility may also be
possible.
Nonlimiting examples of G are: phenyl, biphenyl, naphthyl,
phenanthryl, anthracenyl, benzyl, benzoyl, naphthoyl, phenoxy,
phenoxyphenyl, phenoxybenzoyl, alkyl, alkyl ketone, aryl, aryl
ketone, aralkyl, alkaryl, alkoxy, aryloxy, alkyl ester, aryl ester
(esters may be C-bound or O-bound), amide, alkyl amide, dialkyl
amide, aryl amide, diaryl amide, alkyl aryl amide, amides of cyclic
amines such as piperidine, piperazine and morpholine (amides may be
CO-bound or N-bound), alkyl ether, aryl ether, alkyl sulfides, aryl
sulfides, alkyl sulfones, aryl sulfones, thioether, fluoro,
trifluoromethyl, perfluoroalkyl, and pyridyl, where alkyl is a
linear or branched hydrocarbon chain having between 1 and 30 carbon
atoms, and aryl is any single, multiple or fused ring aromatic or
heteroaromatic group having between 3 and 30 carbon atoms.
Flourine-substituted analogs of the above-identified side groups
may also be used.
G.sub.1 and G.sub.2, and/or G.sub.3 and G.sub.4 may be
interconnected to form bridging groups. Nonlimiting examples of
such groups and the monomer units that result are shown below:
##STR11##
Solubilizing side groups G may also be oligomeric or polymeric
groups. Using side groups which are functionally equivalent to the
flexible polymer to be strengthened increases the compatibility of
the rigid segments with the flexible segments. A nonlimiting
example is the use of a macromonomer, denoted "M.sub.oligo,"
bearing oligocaprolactam side groups G, as a comonomer with
caprolactam in the preparation of
poly(hexamethyleneadipamide-co-M.sub.oligo).
For cases where the monomer unit of the macromonomer is
unsymmetrical about the plane perpendicular to the polymer axis and
centered on the monomer unit, for example if G.sub.1 is benzoyl and
G2, G.sub.3, and G.sub.4, are hydrogen, isomeric forms of the
macromonomer exist. The monomers can link exclusively head-to-tail
to form a regular structure. The monomers can also form a regular
structure by linking exclusively head-to-head and tail-to-tail.
Other more complicated structures and a random structure are also
possible. The particular monomers and conditions used to form the
macromonomer will determine the detailed structure. As used herein,
structures (1), (2) and (3) represent all isomeric cases, either
regular or random.
More than one type of monomer may be used to prepare the
macromonomers of the present invention. Depending on the monomer
used and the conditions of preparation, the resulting macromonomer
may be a random copolymer or it may have additional order, as in a
block, diblock, multiblock, or alternating copolymer.
Copolymerization is a convenient way to adjust the number and type
of side groups G.
It will sometimes be desirable to include 1,4-di-chlorobenzene as a
comonomer, so that some monomer units will be unsubstituted, i.e.,
G.sub.1 .dbd.G.sub.2 .dbd.G.sub.3 .dbd.G.sub.4 .dbd.H. The
unsubstituted units will increase stiffness, but lower solubility.
Unsubstituted monomer units will also lower cost.
Reactive End Groups
The reactive end groups, E, are chosen to allow copolymerization
with the flexible polymer to be stiffened or strengthened. In one
embodiment of the invention, an end group is interconnected with
the main chain of the rigid-rod macromonomer by reacting a chemical
moiety referred to herein as an "endcap" or "endcapper" during or
after polymerization of the monomer units that form the main chain
of the macromonomer.
Reactive end groups can be further derivatized to provide
additional examples of end functionality E, as for example during
deprotection, or transformation of one reactive group into another,
for example reduction of a nitrile into an amine, or an aldehyde
into an alcohol, or an amine into an imine. More than one type of
end group may be present. For example, if three different
endcappers are used during preparation of the macromonomer, a
distribution of end groups will result.
The relative reactivity of endcapper and monomer must also be taken
into account during macromonomer preparation. If the endcapper is
significantly more reactive than the monomer it will be depleted
before the monomer, resulting in some chains without end groups and
an irregular molecular weight distribution. The endcapper may be
added after the reaction has proceeded to a desired molecular
weight, as determined for example by viscosity; however, in this
case excess endcapper may be used, and there may be formation of
some "endcapper dimer." If the endcapper is inexpensive, the dimer
may be tolerated and, if necessary, removed in a later purification
step.
It should be noted that impurities and side reactions will act to
limit the molecular weight and will result in some of the end
groups being different from the desired group E. It will often be
the case that many chains are terminated at one, and to a lesser
extent both, ends by non-reactive end groups derived from
adventitious endcappers or side reactions. This will not usually
detract from the utility of the rigid-rod macromonomers of the
present invention. The small amount of macromonomer chains having a
single reactive endgroup will still be able to participate in later
processing. The even smaller amount with both ends non-reactive is
not likely to macrophase separate due to its low concentration and
affinity toward the larger amount of doubly terminated
macromonomers.
It may be desirable to prepare macromonomers having several types
of reactive end groups. This may be accomplished by adding several
different endcappers during synthesis of the macromonomer. It may
be desired that the different end groups have varying degrees of
reactivity. It may also be desired that each macromonomer have only
one reactive end group, the other being relatively inert. If two
endcappers are used during macromonomer synthesis, typically a
statistical distribution of end groups will result, consistent with
the relative reactivities of the endcappers and the growing
macromonomer chain. Such a statistical distribution may be
separated by methods known in the art, for example chromatography,
to yield substantially pure samples of macromonomers having two end
groups, E and E'. Macromonomers with a single reactive end group
and a single inert end group may be useful in addition
polymerizations where crosslinking must be avoided.
If the macromonomer is prepared using a transition metal catalyst,
and the synthesis proceeds through metallo-terminated chains as
intermediates, the molecular weight of the resulting macromonomer
may be controlled by the catalyst-to-monomer ratio. In this case
the polymerization will cease when the number of chain ends (capped
with catalyst) equals the number of catalyst molecules initially
present. The DP.sub.n will equal twice the monomer to catalyst
ratio. End groups E then may be introduced by adding reagents which
displace the metallo end groups. The metallo-terminated
macromonomer is thereby quenched. Introducing end groups by
quenching avoids any problems of relative rates of endcapper and
monomer.
A macromonomer bearing a particular end group, for example, an
amine or alcohol, may be prepared by first endcapping or quenching
with a precursor which is subsequently transformed into the desired
end group. The precursor group need not be an amine or alcohol,
e.g., and may be unrelated to the final end group except that an
appropriate chemical transformation exists to convert the precursor
to, e.g., an amine or alcohol. For example, a fluorobenzophenone
precursor group can be converted into a variety of amines or
alcohols by nucleophilic displacement of fluoride.
Amines form an important class of end groups. Amine-terminated
macromonomers can be used with polyamides, polyimides,
polyimidamides, polyureas, polyimines, and other polymers derived
from bisamine monomers. Amine-terminated macromonomers can also be
used with polymers not derived from bisamine monomers, such as
epoxides and polyesters; in the latter case the macromonomer would
be incorporated into the polyester chain via amide links.
Preparation of the amine terminated macromonomers can involve
protection/ deprotection of the amine groups, for example as a
succinimide, or an amide.
The following are nonlimiting examples of amine derived end groups:
amino, aminoalkyl, aminoaryl, aminoalkaryl, aminoaralkyl, aniline,
c-alkylaniline, N-alkylaniline, aminophenoxy, and aminobenzoyl.
Other substituted and/or chemically protected aniline side groups
may also be used. The following structures illustrate non-limiting
examples of amine-derived end groups. Typical amines, amino alkyls,
and amino aralkyls are given by the following structures (4a-4d):
##STR12##
where R and R' may be independently chosen from: hydrogen, alkyl,
aryl, alkaryl, aralkyl, alkylketone, arylketone, alkylether or
arylether, where alkyl and aryl are as defined above, x ranges from
one to about twenty, and X is a difunctional group chosen from:
nil, phenyleneoxy, ketophenylene, phenylenesulfone, --O--, --NH--,
keto, --SO.sub.2 --, aryl, alkyl, alkaryl, or aralkyl. R and R'
include bridging groups, such as --CH.sub.2 CH.sub.2 CH.sub.2
CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --,
and --CH.sub.2 CH.sub.2 CH.sub.2 CO--. R and R' will often be used
as protecting groups, to be removed at a later stage of processing,
and as such include common amine and alcohol protecting groups,
nonlimiting examples of which are: trimethylsilyl, trityl,
tetrahydropyranyl, tosyl, methoxyisopropylidene, imide, imine,
amide, ester, and the like.
Typical amino aryl end groups, E, have the structures (5a-5c):
##STR13## where X, R, R' and the groups G.sub.1 through G.sub.4 are
as defined above. Aniline end groups have the above structure where
X is nil and the G's are all hydrogen.
Aminophenoxyphenyl and aminobenzophenone end groups have the
general structures (6a and 6b): ##STR14## where R and R' are as
defined above.
It should be noted that some endcappers can react to form dimers.
The extent of such reactions is determined by the ratio of
endcapper to monomer, and is usually very small. This is usually
not of significance, however, certain endcappers, for example
N-(4-chlorophenyl)-succinimide, will, when dimerized, form
benzidine or benzidine derivatives, which are highly toxic. If such
materials are used proper precautions should be taken. Where
possible such materials should be avoided.
The imides comprise a second class of end groups. The maleimides
are represented by the structures 4a-6b, where R and R' together
equal the bridging group --COCH.dbd.CHCO--. Bismaleimides are
commercially valuable in thermoset resins. Rigid-rod macromonomers
with maleimide end groups are useful for strengthening conventional
bismaleimide resins. They may also be used alone as novel
bismaleimide resins containing rigid-rod elements. Other reactive
imide end groups are contemplated by the present invention,
including the nadimide end groups. Unreactive imides may also be
used; succinimide may be used as a protected form of amine.
Closely related to the amines are the amides. In structures 4a-6b,
if R or R'=--COalkyl or --COaryl, end groups are amides. If R or
R'=--COCH.dbd.CH.sub.2, the end groups are acrylamides. Amide
functionalized macromonomers are also useful in reinforcing
polyamides, such as nylon. Amide groups may react by transamination
with the flexible polymer during polymerization or compounding.
Another important class of reactive end groups are alcohols and
ethers. Diol-capped macromonomers may be used as comonomers with
other diol monomers. Polyesters, polycarbonates, urethanes, and
polyethers are nonlimiting examples of polymers prepared from
diols. Alcohol macromonomers may also be used in non-diol derived
polymers, for example, polyamides, where linkage to the
macromonomer is through ester links. Both the amine macromonomers
and the alcohol macromonomers may be used to replace dibasic
monomers, in general, in condensation polymerizations.
Nonlimiting examples of alcohol-terminated macromonomers are:
hydroxy, hydroxyalkyl, hydroxyaryl, hydroxyalkaryl, hydroxyaralkyl,
phenol, C-alkylphenol, o-alkylphenol, hydroxyphenoxy, and
hydroxybenzoyl. The following nonlimiting structures (7a-7d)
illustrate exemplary alcohol end groups: ##STR15## where R, x and X
are as defined in the discussion following structures (4a-4d).
The following structures (8a-8c) are representative of phenolic end
groups: ##STR16## where G.sub.1 -G.sub.4, R, and X are as defined
above.
The following structures (9a-9c) are more specific examples of the
above structures: ##STR17## where R is as defined above.
For R.dbd.H, the structures (9a-9c) represent phenol,
hydroxyphenoxyphenyl, and hydroxybenzophenone end groups,
respectively. For R=ketoalkyl or ketoaryl, the structures (9a-9c)
are phenylesters. R may contain additional reactive groups, such as
acrylate or vinyl. In structures 7a through 9c, for
R=--COCH.dbd.CH.sub.2 the end groups are acrylates, for
R=--CH.dbd.CH.sub.2 the end groups are vinyl ethers.
Carbonyl-containing reactive end groups including acetyl, formyl,
carboxy, ester, amide, acrylate, ketoalkyl and ketoaryl are
represented by the structures (10a-10d) where Y is CH.sub.3, H, OH,
OR, NRR', vinyl, alkyl and aryl respectively, and G.sub.1 -G.sub.4
and X are as defined above. Amides may be C- or N-bound; see
structures 4a-6b above ##STR18## Macromonomers of the present
invention having carboxy end groups may be used to reinforce
polyesters, polycarbonates, and polyamides.
Acetylene end groups have the structures (11a-11d) where Y is
--CCH. Olefin end groups have the structures (11a-11d) where Y is
--CH.dbd.CH.sub.2. Halide, cyano, cyanate, and isocyanate end
groups have the structures (11a-11d) where Y is -halogen, --CN,
--OCN and --NCO respectively. ##STR19##
Reactive end groups may also be strained ring compounds including
epoxides, biphenylenes and benzocyclobutenes.
In situations where the reactive end groups E are reactive with
each other, both the end groups E and the groups on the flexible
polymer or monomer with which they are ultimately to react should
be selected so that the relative rates of reaction are
approximately equal. This will enhance the randomness of the
distribution of the macromonomer within the final polymer.
When the rigid-rod macromonomers of the present invention are used
as pre-polymerization additives, they are preferably added in an
amount such that W.sub.r ranges from 1 percent to 60 percent, i.e.,
the rigid-rod macromonomers make up from 1 percent to 60 percent of
the weight of the resulting polymeric material. Such a range takes
into account the trade off between increased cost and decreased
processability that results as the value of W.sub.r increases in
magnitude. In practice, it is desirable to experimentally determine
the optimal weight fraction required for particular
applications.
In certain circumstances, it may be desirable for W.sub.r to exceed
60 percent of the total weight of the copolymeric material. For
instance, when the rigid-rod macromonomers of the present invention
are used alone as thermosetting resins, W.sub.r can approach the
limiting value of 100 percent, depending on the size, frequency,
and orientation of the crosslinking groups formed during curing. In
addition, suitable endcapped macromonomers could be utilized to
prepare new rigid-rod copolymers wherein all of the segments are
rigid. For instance, if a macromonomer with amino endgroups were
reacted with pyromellitic dianhydride (PMDA), the resulting
copolymer would be a rigid-rod after complete imidization. The
polyamic acid prepolymer should retain reasonable processability
and could be fabricated into desirable shapes before effecting
imidization to the final rigid-rod polymer.
There will also be an optimal range for L.sub.r, typically between
8 and 500 repeat units, beyond which additional increases in length
will have little further effect on strength or stiffness but will
reduce processability. Optimal ranges for both W.sub.r and L.sub.r
can be readily determined by one skilled in the art.
The aspect ratio of the macromonomers incorporated into copolymers
also affects the physical properties of the copolymers,
particularly the processability thereof. The aspect ratio of a
macromonomer is defined to be the length to diameter ratio of the
smallest diameter cylinder which will enclose the macromonomer
segment, including half the length of the terminal connecting
bonds, including hydrogen but not any attached side groups, such
that the axis of the cylinder is parallel to the connecting bonds
in the straight segment.
For rigid-rod polyphenylenes, and aza analogs, the aspect ratio is
approximately equal to the DP.sub.n, because the phenylene monomer
unit has an aspect ratio of about one.
When the average aspect ratio of the macromonomers is less than
about 7 or 8, the macromonomers typically do not impart the desired
strength and stiffness into the final polymer. As the aspect ratio
is increased, the mechanical properties of the reinforced polymer
improve. All other factors being equal, a longer rigid-rod segment
will provide a greater increase in stiffness than a shorter
rigid-rod segment. This is true for reinforcement of any
geometrical type of polymer, e.g., linear, branched, crosslinked,
and so forth. It is known in the art that for conventional
fiber-containing composites mechanical properties improve rapidly
up to aspect ratios of about 100, after which there are lesser
improvements. A similar situation has been found to exist for
rigid-rod macromonomers.
Although mechanical properties of the polymers improve as the
aspect ratio increases, processing becomes more difficult.
Viscosities of polymer solutions are dependent on the DP.sub.n of
the polymer. Viscosities of rigid-rod polymers increase much more
rapidly with DP.sub.n than viscosities of flexible polymers.
Similarly, melt viscosities of flexible polymers reinforced with
rigid-rod polymers increase with the DP.sub.n of the rigid
segments, making thermal processing more difficult as DP.sub.n
increases.
There is generally a trade-off between improved mechanical
properties and difficulty of processing, resulting in an optimal
aspect ratio and DP.sub.n for the rigid-rod macromonomers. For
example, if it is desired to increase the modulus of a flexible
polymer reinforced with rigid-rod macromonomers, the aspect ratio
of the macromonomer could be increased, but the melt and solution
viscosity will increase and solubility of the rigid-rod
macromonomer will decrease, making processing and preparation more
difficult. DP.sub.n 's of about 100 are often optimal; however,
higher or lower DP.sub.n 's may sometimes be desirable.
The following procedures provide three exemplary methods for
preparing the rigid-rod macromonomers of the present invention, an
exemplary method of preparing succinimide-protected amines, and
other synthetic methods used in the present invention. More
specific methods are given below in the Examples, which refer to
the General Procedures. The choices and amounts of reagents,
temperatures, reaction times, and other parameters are
illustrative, but are not considered limiting in any way. Other
approaches are contemplated by, and within the scope of, the
present invention.
It will also be recognized by one skilled in the art that for any
given procedure certain functionalities will not be tolerated. For
example, in General Procedures I-III protic side groups, end
groups, solvents, or any source of acidic protons are not
tolerated. Other procedures, e.g., that of Example 67 using a
palladium catalyst, will tolerate protic groups and solvents. As a
second example, nickel catalyzed couplings are known to be
sensitive to nitro groups and ortho-dihalo groups.
For the nickel catalyzed coupling reactions used here, many
variations on catalyst composition, accelerators, solvent, reducing
agent, order of addition, and the like are possible. For example,
phosphines other than triphenylphosphine have been used with nickel
coupling catalysts, including triethylphosphine and
bis(diphenylphosphino)ethane; electrochemical reduction has been
used as an alternative to zinc; accelerators have included
chloride, bromide, iodide, and aromatic nitrogen heterocycles such
as 2,2'-bipyridine; and solvents have included ethers, acetone,
dimethylformamide, and acetonitrile.
General Procedure --I. (Preparation of Macromonomer by Simultaneous
Addition of Monomer and Endcapper)
Anhydrous bis(triphenylphosphine) nickel(II) chloride (0.25 g; 0.39
mmol), triphenylphosphine (0.60 g; 2.29 mmol), sodium iodide (0.175
g, 1.17 mmol), and 325 mesh activated zinc powder (approximately
1.5 mmol / mmol monomer) are placed into a 25 ml flask under an
inert atmosphere along with 7 ml of anhydrous N-methylpyrrolidinone
(NMP). This mixture is stirred for about 10-20 minutes, leading to
a deep-red coloration. A solution of between 3-20 mmol of monomer
and between about 0.3 to 2.5 mmol endcapper in 8 ml of anhydrous
NMP is then added by syringe. After stirring for about 12-60 hours
at 50.degree.-60.degree. C., the resulting viscous solution is
poured into 100 ml of 1 molar hydrochloric acid in ethanol to
dissolve the excess zinc metal and to precipitate the macromonomer.
This suspension is filtered and the precipitate triturated with
acetone and dried to afford a light yellow to white powder in
40-99% yield.
General Procedure --II. (Preparation of Macromonomer by Slow
Addition of Endcapper to Monomer)
Anhydrous bis(triphenylphosphine) nickel(II) chloride (0.25 g, 0.39
mmol), triphenylphosphine (0.60 g; 2.29 mmol), sodium iodide (0.175
g, 1.17 mmol), and 325 mesh activated zinc powder (approximately
1.5 mmol / mmol monomer) are placed into a 25 ml flask under an
inert atmosphere along with 7 ml of anhydrous
N-methyl-pyrrolidinone (NMP). This mixture is stirred for about
10-20 minutes, leading to a deep-red coloration. A solution of
between 3-20 mmol of monomer in 8 ml of anhydrous NMP is then added
all at once by syringe, and between 0.3 to 2.5 mmol endcapper in 5
ml of anhydrous NMP is then added dropwise by syringe over a period
ranging from about 15 to about 60 minutes with the reaction mixture
held at 50.degree.-60.degree. C. After stirring for about 12-60
hours, the resulting viscous solution is poured into 100 ml of 1
molar hydrochloric acid in ethanol to dissolve the excess zinc
metal and to precipitate the macromonomer. This suspension is
filtered and the precipitate triturated with acetone and dried to
afford a light yellow to white powder in 40-99% yield.
General Procedure --III. (Preparation of Macromonomer by Adding
Endcapper to Monomer at End of Reaction)
Anhydrous bis (triphenylphosphine) nickel (II) chloride (0.25 g,
0.39 mmol), triphenylphosphine (0.60 g; 2.29 mmol), sodium iodide
(0.175 g, 1.17 mmol), and 325 mesh activated zinc powder
(approximately 1.5 mmol / mmol monomer) are placed into a 25 ml
flask under an inert atmosphere along with 7 ml of anhydrous
N-methyl-pyrrolidinone (NMP). This mixture is stirred for about
10-20 minutes, leading to a deep-red coloration. A solution of
between 3-20 mmol of monomer in 8 ml of anhydrous NMP is then added
all at once by syringe and the reaction mixture brought to
50.degree.-60.degree. C. After a period ranging from about 15
minutes to about 24 hours (depending on the reactivity of the
monomer), a large excess (at least about 5-10 mmol) of endcapper is
then added by syringe. Typically the color of the reaction mixture
will become green upon addition of the monomer and then evolve
through orange and then back to red as the monomer is consumed. The
endcap is optimally added just as the reaction begins to develop
the orange coloration. After stirring for about 12-60 hours, the
resulting viscous solution is poured into 100 ml of 1 molar
hydrochloric acid in ethanol to dissolve the excess zinc metal and
to precipitate the macromonomer. This suspension is filtered and
the precipitate triturated with acetone and dried to afford a light
yellow to white powder in 40-99% yield.
The above procedures I-III describe macromonomer formation by
reductive coupling of monomer precursors, e.g., substituted
1,4-dihaloaromatic compounds, in the presence of a catalyst, and
reaction with endcappers.
For the nickel catalyzed coupling reactions described in General
Procedures I-III, it is believed that before quenching or workup,
the nickel catalyst resides at the end of the chain, and on
completion of reaction functions as a chain terminator. Therefore,
the length of the macromonomer chain will be largely determined by
the molar ratios of monomer (U), endcapper (E) and catalyst (C):
##STR20## where m, e and c are the number of moles of monomer,
endcapper and catalyst, respectively.
Those skilled in the art will recognize that the DP.sub.n at the
completion of the macromonomer-forming reaction can be calculated
using the Carothers equation. Assuming no chain limiting
impurities, equal reactivity of monomer and endcapper, and that end
groups E are not counted when calculating DP.sub.n, the Carothers
equation for General Procedures I and II simplifies to:
Procedure III largely depends upon quenching the nickel-terminated
polymer chains with an excess of endcapper so the degree of
polymerization does not depend on e (because initially e=0), and
thus:
Methods for calculating required ratios of monomer, endcapper,
catalyst, etc. given a desired DP.sub.n are known in the art for
various types of polymerization reactions and conditions. It is
often useful to experimentally determine the extent of reaction, p,
by preparing a polymer in the absence of endcapper and measuring
DP.sub.n. The extent of reaction p is then given by:
This experimentally determined p may then be used by methods known
in the art to calculate the molar amounts of monomer and endcapper
required.
Of course, DP.sub.n or any other property, such as viscosity, may
be adjusted by trial and error, varying ratios of monomer,
endcapper and catalyst experimentally to identify the desired
range.
General Procedure --IV. (Preparation of succinimide protected
amines)
The dry amine (0.5 mol) and succinic anhydride (0.5 mol) are
dissolved in 2.sub.L dry toluene. Catalyst, p-toluenesulfonic acid
(0.01 mol), is then added and the mixture is held at reflux for 24
hours, using a Dean-Stark trap to collect water. After cooling, the
product is precipitated with diethyl ether, filtered, washed with
ether and dried.
General Procedure --V. (Removal of protecting groups)
In the cases where the functional end group is protected as an
imide, amide, or ester, the protecting groups are removed as
follows: The protected macromonomer is suspended in 25 ml of 10%
HCl in ethanol and heated to reflux for six to twelve hours. This
mixture is neutralized with sodium hydroxide, filtered, washed and
dried. Further purification by dissolution and precipitation by
adding a non-solvent may be effected.
Preparation of 2,5-Dichlorobenzoyl Compounds
2,5-dichlorobenzoyl-containing compounds (e.g.
2,5-dichlorobenzophenones and 2,5-dichlorobenzamides) can be
readily prepared from 2,5-dichlorobenzoylchloride. Pure
2,5-dichlorobenzoylchloride is obtained by vacuum distillation of
the mixture obtained from the reaction of commercially available
2,5-dichlorobenzoic acid with a slight excess of thionyl chloride
in refluxing toluene. 2,5-dichlorobenzophenones
(2,5-dichlorobenzophenone,
2,5-dichloro-4'-methylbenzophenone,2,5-dichloro-4'-meth-oxybenzophenone,
and 2,5-dichloro-4'-phenoxy-benzo-phenone) are prepared by the
Friedel-Crafts benzoylations of benzene and substituted benzenes
(e.g. toluene, anisole, diphenyl ether), respectively, with
2,5-dichlorobenzoylchloride at 0.degree.-5.degree. C. using 2-3 mol
equivalents of aluminum chloride as a catalyst. The solid products
obtained upon quenching with water are purified by
recrystallization from toluene/hexanes.
2,5-dichlorobenzoylmorpholine and 2,5-dichloro-benzoylpiperidine
are prepared from the reaction of 2,5-dichlorobenzoylchloride and
either morpholine or piperidine, respectively, in toluene with
pyridine added to trap the HCl that is evolved. After washing away
the pyridinium salt and any excess amine, the product is
crystallized from the toluene solution.
Preparation of Activated Zinc Powder
Activated zinc powder is obtained after 2-3 washings of
commercially available 325 mesh zinc dust with 1 molar hydrogen
chloride in diethyl ether (anhydrous) and drying in vacuo or under
inert atmosphere for several hours at about 100.degree.-120.degree.
C. This material should be used immediately or stored under an
inert atmosphere away from oxygen and moisture.
The following specific examples are illustrative of the present
invention, but are not considered limiting thereof in any way.
EXAMPLE 1
Preparation of a macromonomer of the structure (1), where G.sub.1
is p-toluyl (--COC.sub.6 H.sub.4 --4--CH.sub.3), G.sub.2 through
G.sub.4 are hydrogen, E is 3-carbomethoxyphenyl (--C.sub.6 H.sub.4
(COOCH.sub.3)), and DP.sub.n .apprxeq.7.
Anhydrous bis(triphenylphosphine)nickel(II) chloride (0.505 g; 0.77
mmol), triphenylphosphine (0.40 g; 1.53 mmol), sodium iodide (0.175
g, 1.17 mmol), and 325 mesh activated zinc powder (1.0 g, 15.3
mmol) were placed into a 25 ml flask under an inert atmosphere
along with 7 ml of anhydrous N-methylpyrrolidinone (NMP). This
mixture was stirred for about 10-20 minutes, leading to a deepred
coloration. A solution of 2,5-dichloro-4'-methylbenzophenone (1.84
g; 6.94 mmol) and methyl-3-chlorobenzoate (0.32 g; 1.88 mmol) in 8
ml of anhydrous NMP was then added by syringe. After stirring for
about 18 hours at 50.degree. C., the reaction mixture was poured
into 100 ml of 1 molar hydrochloric acid in ethanol to dissolve the
excess zinc metal and to precipitate the macromonomer. This
suspension was filtered and the precipitate triturated with acetone
and dried to afford a 42% yield of the macromonomer. Analysis of
the macromonomer by size exclusion chromatography (SEC) indicated a
weight average molecular weight (relative to polystyrene) of 14,000
with a polydispersity of 1.4. Proton nuclear magnetic resonance
(.sup.1 H NMR; 500 MHz) spectroscopy indicated that the
macromonomer consisted of a monomer-to-endcap ratio of 8.8:1.
EXAMPLE 2
Preparation of a macromonomer of the structure (1), where G.sub.1
is p-toluyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-carbomethoxyphenyl, and DP.sub.n .apprxeq.7.
The procedure of Example 1 was followed, except that an additional
0.33 g of methyl-3-chlorobenzoate was added to the reaction mixture
after about 3 hours at 50.degree. C. After 4.5 hours, the reaction
mixture was worked up as in Example 1 to afford a 48% yield of the
macromonomer. SEC analysis (relative to polystyrene) indicated
M.sub.w =15,600 and polydispersity of 1.5.
EXAMPLE 3
Preparation of a macromonomer of the structure (1), where G.sub.1
is p-toluyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-carbomethoxyphenyl, and DP.sub.n .apprxeq.7.
The procedure of Example 2 was followed, except that the additional
0.33 g of methyl-3-chlorobenzoate was added after about 18 hours.
After 24 hours, the reaction mixture was worked up as before to
afford a 43% yield of the macromonomer. SEC analysis (relative to
polystyrene) indicated M.sub.w =14,000 and polydispersity of
1.4.
EXAMPLE 4
Preparation of a macromonomer of the structure (1), where G.sub.1
is p-toluyl, the G.sub.2 through G.sub.4 are hydrogen, E is
3-carbomethoxyphenyl, and DP.sub.n .apprxeq.16.
General Procedure I was followed, where the monomer was
2,5-dichloro-4'-methylbenzophenone (2.55 g; 9.62 mmol), the
endcapper was methyl-3-chlorobenzoate (0.16 g; 0.96 mmol), and 1.0
g (15.3 mmol) of zinc was used. After 18 hours the reaction was
worked up to afford a 69% yield of the macromonomer. SEC analysis
(relative to polystyrene) indicated M.sub.w =29,500 and
polydispersity of 3.0.
EXAMPLE 5
Preparation of a macromonomer of the structure (1), where G.sub.1
is p-toluyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-carbomethoxyphenyl, and DP.sub.n .apprxeq.30.
General Procedure I was followed, where the monomer was
2,5-dichloro-4'-methylbenzophenone (5.11 g; 19.27 mmol), the
endcapper was methyl-3-chlorobenzoate (0.16 g; 0.96 mmol), and 2.0
g (39.7 mmol) of zinc was used. After 18 hours the reaction was
worked up to afford a greater than 90% yield of the macromonomer.
SEC analysis (relative to polystyrene) indicated M.sub.w =54,000
and polydispersity of 3.9. Proton nuclear magnetic resonance
(.sup.1 H NMR; 500 MHz) spectroscopy indicated that the
macromonomer consisted of a monomer-to-endcap ratio of 34:1.
EXAMPLE 6
Preparation of a macromonomer of the structure (1), where G.sub.1
is p-toluyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-carbomethoxyphenyl, and DP.sub.n .apprxeq.30.
The procedure of Example 5 was followed, but an additional 0.16 g
of the methyl-3-chlorobenzoate endcapper was added to the reaction
mixture after 6 hours. After 18 hours the reaction was worked up to
afford a 95% yield of the macromonomer. SEC analysis (relative to
polystyrene) indicated M.sub.w =66,000 and polydispersity of
3.8.
EXAMPLE 7
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-carbomethoxyphenyl, and DP.sub.n .apprxeq.16.
Anhydrous bis (triphenylphosphine) nickel (II) chloride (5.04 g;
7.7 mmol), triphenylphosphine (12 g; 45.75 mmol), sodium iodide
(3.5 g, 23.35 mmol), and 325 mesh activated zinc powder (20 g, 306
mmol) were placed into a 500 ml round-bottom flask under an inert
atmosphere along with 140 ml of anhydrous N-methylpyrrolidinone
(NMP). This mixture was stirred for about 10-20 minutes, leading to
a deep-red coloration. A solution of 2,5-dichlorobenzophenone
(48.36 g; 193 mmol) and methyl-3-chlorobenzoate (3.28 g; 19.2 mmoi)
in 160 ml of anhydrous NMP was then added. After stirring for about
3 days at 50.degree. C., the viscous reaction mixture was poured
into 700 ml of 1 molar hydrochloric acid in ethanol to dissolve the
excess zinc metal and to precipitate the macromonomer. This
suspension was filtered and the precipitate triturated with acetone
and dried to afford a 62% yield of the macromonomer. Analysis of
the macromonomer by SEC indicated a weight average molecular weight
(relative to polystyrene) of 37,000 with a polydispersity of
1.9.
EXAMPLE 8
Preparation of a macromonomer of the structure (1), where G.sub.1
is p-toluyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-carbomethoxyphenyl and DP.sub.n .apprxeq.10.
General Procedure III was followed, where the monomer was
2,5-dichloro-4'-methylbenzophenone (2.55 g, 9.62 mmol) and the
endcapper, methyl-3-chlorobenzoate (0.164 g; 0.96 mmol), was added
after a period of 25 minutes. After stirring for about 18 hours,
the viscous reaction mixture was poured into 100 ml of 1 molar
hydrochloric acid in ethanol to dissolve the excess zinc metal and
to precipitate the macromonomer. This suspension was filtered and
the precipitate triturated with acetone and dried to afford a 66%
yield of the macromonomer. Analysis of the macromonomer by SEC
indicated a weight average molecular weight (relative to
polystyrene) of 19,000 with a polydispersity of 2.1.
EXAMPLE 9
Preparation of a macromonomer of the structure (1), where G.sub.1
is p-anisoyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-acetylphenyl, and DP.sub.n .apprxeq.16.
General Procedure II is followed, where the monomer is
2,5-dichloro-4'-methoxybenzophenone (2.4 g, 8.37 mmol) and the
endcapper, 3-chloroacetophenone (119 mg, 0.77 mmol), is added over
about 15 minutes to yield the acetyl-functionalized
macromonomer.
EXAMPLE 10
Preparation of a macromonomer of the structure (1), where G.sub.1
is p-anisoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-acetylphenyl, and DP.sub.n .apprxeq.41.
General Procedure II is followed, where the monomer is
2,5-dichloro-4'-methoxybenzophenone (4.8 g, 16.74 mmol) and the
endcapper is 4-chloroacetophenone (63 mg, 0.44 mmol), which is
added dropwise over a period of about 30 minutes, to yield the
acetyl-functionalized macromonomer.
EXAMPLE 11
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-acetylphenyl, and DP.sub.n .apprxeq.22.
General Procedure III is followed, where the monomer is
2,5-dichlorobenzophenone (1.1 g, 4.38 mmol) and the endcapper is
4-chloroacetophenone (1 ml, 7.7 mmol), which is added all at once
after a period of 20 minutes, to yield the acetyl-functionalized
macromonomer.
EXAMPLE 12
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-formylphenyl, and DP.sub.n .apprxeq.11.
General Procedure II is followed, where the monomer is
2,5-dichlorobenzophenone (1.1 g, 4.38 mmol) and the endcapper is
3-chlorobenzaldehyde (70 mg, 0.5 mmol) in 5 ml of anhydrous NMP,
which is added over a period of about 30 minutes, to yield the
formyl-functionalized macromonomer.
EXAMPLE 13
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-carbophenoxyphenyl, and DP.sub.n .apprxeq.13.
General Procedure I is followed, where the monomer is
2,5-dichlorobenzophenone (2.89 g; 11.5 mmol) and the endcapper is
phenyl-3-chlorobenzoate (0.40 g, 1.72 mmol) to yield the
ester-functionalized macromonomer.
Phenyl-3-chlorobenzoate is prepared by reacting 3-chlorobenzoyl
chloride with phenol in toluene with some pyridine (1 mol
equivalent per acid chloride) to trap the HCl that evolves. After
aqueous extraction of the pyridinium salt and any excess starting
materials, the product is crystallized from the toluene
solution.
EXAMPLE 14
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-(N,N-dimethylcarbamyl)phenyl, and DP.sub.n .apprxeq.17.
The procedure of Example 13 is followed, but the endcapper is
4-chloro-N,N-dimethylbenzamide (0.20 g, 1.09 mmol) to yield the
amido-functionalized macromonomer. 4-Chloro-N,N-dimethylbenzamide
is prepared by reacting 4-chlorobenzoyl chloride with dimethylamine
in toluene with some pyridine (1 mol equivalent per acid chloride)
to trap the HCl that is evolved. After aqueous extraction of the
pyridinium salt and any excess starting materials, the product is
crystallized from the toluene solution.
EXAMPLE 15
Preparation (1), where G.sub.1 is benzoyl, G.sub.2 through G.sub.4
are hydrogen, E is 4-acrylylphenyl (4-C.sub.6 H.sub.4
COCHCH.sub.2), and DP.sub.n .apprxeq.28.
The procedure of Example 13 is followed, but the endcapper is
4'-chloro-3-dimethylaminopropiophenone (0.10 g, 0.47 mmol) to yield
the ketone-functionalized macromonomer. The product has structure
1, where G.sub.1 is benzoyl, G.sub.2 through G.sub.4 are hydrogen,
E is 4'-(3-di-methyl-aminopropionyl) phenyl, and DP.sub.n
.apprxeq.28. This oligomer can be converted to the more useful
acrylyl-terminated form by thermally induced loss of dimethylamine.
4'-Chloro-3-dimethylaminopropiophenone is prepared by treating
4'-chloro-3-dimethylaminopropiophenone hydrochloride with aqueous
base to remove the HCl. The free amine is extracted into diethyl
ether and recovered by evaporation of the solvent. The
hydrochloride salt is prepared by the method of Maxwell in Org.
Synth. Coll. Vol. III, 305-306. Thus, a mixture of
4-chloroace-tophenone, dimethylamine hydrochloride, and
paraformaldehyde is refluxed for 2-4 hours in 95% ethanol with a
small amount of added hydrochloric acid. The solid product is
obtained after adding acetone and cooling overnight.
EXAMPLE 16
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-cyanophenyl, and DP.sub.n .apprxeq.34.
General Procedure II is followed, where the monomer is
2,5-dichlorobenzophenone (2.89 g; 11.5 mmol) and the endcapper is
4-chlorobenzonitrile (41 mg, 0.3 mmol) to yield the
cyano-functionalized macromonomer. 3-Chlorophenyl vinyl ketone is
prepared by thermolysis of 4'-chloro-3-dimethylaminopropiophenone
hydrochloride (see Example 15).
EXAMPLE 17
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-(napthalic-1,8-dianhydride), and DP.sub.n .apprxeq.20-25.
The procedure of Example 11 is followed, where the endcapper is
4-bromo-1,8-naphthalic anhydride (1.5 g, 5.41 mmol) in 10 ml of
anhydrous NMP, which is added all at once after a period of 20
minutes, to yield the anhydride-functionalized macromonomer.
EXAMPLE 18
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-carboxyphenyl, and DP.sub.n .apprxeq.20-25.
The procedure of Example 11 is followed, where the endcapper is
3-iodotoluene (1 ml, 7.79 mmol), which is added all at once after a
period of 30 minutes, to yield the methyl-functionalized
macromonomer. The product has structure 1, where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is 3-tolyl, and
n.apprxeq.20-25. This oligomer can be converted to the more useful
carboxy-terminated form by oxidation.
EXAMPLE 19
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-acrylylphenyl, and DP.sub.n .apprxeq.20-25.
The procedure of Example 11 is followed, where the endcapper is
4-chlorophenyl vinyl ketone (1 ml, 7.79 mmol), which is added all
at once after a period of 15 minutes, to yield the
acrylyl-functionalized macromonomer.
EXAMPLE 20
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is methyl, and
DP.sub.n 20-25.
The procedure of Example 11 is followed, where the endcapper is
methyl iodide (0.5 ml, 8.0 mmol), which is added all at once after
a period of 90 minutes, to yield the methyl-functionalized
macromonomer. This oligomer can be converted to the more useful
carboxy-terminated form by oxidation. The resulting product has
structure 1, where G.sub.1 is benzoyl, the remaining G's are
hydrogen, E is carboxy, and n.apprxeq.20-25.
EXAMPLE 21
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is cyano, and
DP.sub.n .apprxeq.20-25.
The procedure of Example 11 is followed, where the endcapper is
sodium cyanide (0.5 g; 10.2 mmol) in 1 ml of anhydrous NMP, which
is added all at once after a period of 30 minutes, to yield the
cyano-functionalized macromonomer.
EXAMPLE 22
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
N-succinimido, and DP.sub.n .apprxeq.20-25.
The procedure of Example 11 is followed, where the endcapper is
N-bromosuccinimide (NBS) (1 g, 5.6 mmol), which is added all at
once after a period of 30 minutes, to yield the
succinimido-functionalized macromonomer. This oligomer can be
converted to the more useful amino-terminated form by acidic
hydrolysis. The resulting product has structure 1, where G.sub.1 is
benzoyl, the remaining G's are hydrogen, E is amino, and
n.apprxeq.20-25.
EXAMPLE 23
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is acetyl, and
DP.sub.n .apprxeq.20-25.
The procedure of Example 11 is followed, where the endcapper is
acetyl chloride (0.5 ml, 7.0 mmiol), which is added all at once
after a period of 90 minutes, to yield the acetyl-functionalized
macromonomer.
EXAMPLE 24
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is acrylyl, and
DP.sub.n .apprxeq.20-25.
Procedure of Example 11 is followed, where the endcapper is
acryloyl chloride (0.5 ml, 6.2 mmol), which is added all at once
after a period of 90 minutes, to yield the acrylyl-functionalized
macromonomer.
EXAMPLE 25
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
5-carbethoxypentanoyl (COCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2
CO.sub.2 CH.sub.2 CH.sub.3) and DP.sub.n .apprxeq.20-25.
The procedure of Example 11 is followed, where the endcapper is
adipoyl chloride (1 ml, 6.9 mmol), which is added all at once after
a period of 90 minutes, to yield the adipyl-functionalized
macromonomer.
EXAMPLE 26
Preparation of a macromonomer of the structure (1), where G.sub.1
is carbonylmorpholine (-(CO)NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2),
G.sub.2 through G.sub.4 are hydrogen, E is 4-acetylphenyl, and
DP.sub.n .apprxeq.20-25.
General Procedure III is followed, where the monomer is
2,5-dichlorobenzoylmorpholine (1.1 g, 4.23 mmol) and the endcapper
is 4-chloroacetophenone (1 ml, 7.7 mmol), which is added all at
once after a period of 18 hours, to yield the acetyl-functionalized
macromonomer.
EXAMPLE 27
Preparation of a macromonomer of the structure (1), where G.sub.1
is carbonylmorpholine, G.sub.2 through G.sub.4 are hydrogen, E is
3-carbophenoxyphenyl, and DP.sub.n .apprxeq.20-25.
The procedure of Example 26 is followed, where the endcapper is
phenyl-3-chlorobenzoate (1.5 g, 6.4 mmol), which is added all at
once after a period of 8 hours, to yield the ester-functionalized
macromonomer.
EXAMPLE 28
Preparation of a macromonomer of the structure (1), where G.sub.1
is carbonylmorpholine, G.sub.2 through G.sub.4 are hydrogen, E is
4-carbethoxyphenyl, and DP.sub.n .apprxeq.21.
General Procedure I is followed, where the monomer is
2,5-dichlorobenzoylmorpholine (2.5 g, 10.0 mmol) and the endcapper
is ethyl-4-chlorobenzoate (0.1 ml, 0.64 mmol) to yield the
ester-functionalized macromonomer.
EXAMPLE 29
Preparation of a macromonomer of the structure (1), where G.sub.1
is carbonylmorpholine, G.sub.2 through G.sub.4 are hydrogen, E is
4-acrylylphenyl, and DP.sub.n .apprxeq.19.
General Procedure II is followed, where the monomer is
2,5-dichlorobenzoylmorpholine (2.5 g, 10.0 mmol) and the endcapper
is 4'-chloro-3-dimethylaminopropiophenone (0.15 g, 0.71 mmol) to
yield the ketone-functionalized macromonomer. The product has
structure (1), where G.sub.1 is carbonylmorpholine, the remaining
G's are hydrogen, E is 4'-(3-dimethylaminopropionyl)phenyl, and
n.apprxeq.20-25. This oligomer can be converted to the more useful
acrylyl-terminated form by thermally induced loss of
dimethylamine.
EXAMPLE 30
Preparation of a macromonomer of the structure (1), where G.sub.1
is 4-phenoxybenzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-acetylphenyl, and DP.sub.n .apprxeq.27.
General Procedure I is followed, where the monomer is
2,5-dichloro-4'-phenoxybenzophenone (5.0 g, 14.6 mmol) and the
endcapper is 4-chloroacetophenone (0.1 ml, 0.77 mmol) to yield the
acetyl-functionalized macromonomer.
EXAMPLE 31
Preparation of a macromonomer of the structure (1), where G.sub.1
is 4-phenoxybenzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
3-carbophenoxyphenyl, and DP.sub.n .apprxeq.19.
The procedure of Example 30 is followed, where the endcapper is
phenyl-3-chlorobenzoate (0.30 g, 1.3 mmol) to yield the
ester-functionalized macromonomer.
EXAMPLE 32
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
2-(4'-aminobenzophenone), and DP.sub.n .apprxeq.16.
General Procedure I is followed, where the monomer is
2,5-dichlorobenzophenone (11.5 mmol) and the endcapper is
2-chloro-4'-(N-succinimido)benzophenone (1.15 mmol) (prepared in
the manner described below). The resulting macromonomer is in the
protected succinimide form. The free amine is obtained by refluxing
the succinimide with 25 ml of 10% HCl in ethanol for six hours,
followed by neutralization with sodium hydroxide, and extraction
into methylene chloride. The methylene chloride layer is washed
with aqueous base, then water, and ethanol is added to precipitate
the diamine product.
2-Chloro-4'-(N-succinimido)benzophenone is prepared as follows: To
a solution of 2-chloro-4'-fluoro-benzophenone (100 mmol) in NMP
(100 ml) is added succinimide (110 mmol) and potassium carbonate
(200 mmol). After heating at 80.degree. C. for 8 hours, 100 ml of
water is added and the mixture extracted with methylene chloride.
The product is recrystallized from methylene chloride -
ethanol.
EXAMPLE 33
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is 3-aminophenyl,
and DP.sub.n =16.
General Procedure I is followed, where the monomer is
2,5-dichlorobenzophenone (11.5 mmol), and the endcapper is
N-(3-chlorophenyl)succinimide (1.15 mmol) (prepared from
3-chloroaniline using General Procedure IV). The resulting
macromonomer is in the protected succinimide form. The free amine
is obtained by refluxing the succinimide with 25 ml of 10% HCl in
ethanol for six hours, followed by neutralization with sodium
hydroxide, and extraction into methylene chloride. The methylene
chloride layer is washed with aqueous base, then water, and ethanol
is added to precipitate the diamine product.
EXAMPLE 34
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-(2-aminoethyl)phenyl, and DP.sub.n =16.
General Procedure I is followed, where the monomer is
2,5-dichlorobenzophenone (11.5 mmol), and the endcapper is
N-2-(4-chlorophenyl)ethylsuccinimide (1.15 mmol) (prepared from
2-(4-chlorophenyl) ethylamine using General Procedure IV).
Deprotection, as in the general procedure, yields the
amino-functionalized macromonomer.
EXAMPLE 35
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
7-amino-2-fluorenyl, and DP.sub.n =14.
The procedure of Example 32 is followed, where the endcapper is
2-bromo-7-N-succinimidofluorene (1.533 mmol) (prepared from
2-amino-7-bromofluorene using General Procedure IV). Deprotection
yields the amino-functionalized macromonomer.
EXAMPLE 36
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-(2-methoxy-5-methylaniline), and DP.sub.n =19.
The procedure of Example 32 is followed, where the endcapper is the
phthalimide of 4-chloro-2-meth-oxy-5-methylaniline (0.92 mmol).
Deprotection yields a macromonomer having structure 1 where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-(2-methoxy-5-methyl-aniline), and DP.sub.n =19.
EXAMPLE 37
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is 4-phenol, and
DP.sub.n =14.
The procedure of Example 32 is followed, where the endcapper is
4-chlorophenylacetate (1.533 mmol). Deprotection yields the
hydroxy-functionalized macromonomer.
4-Chlorophenyl acetate is prepared by acylation of 4-chlorophenol
with acetic anhydride using Schotten Baumann conditions.
EXAMPLE 38
Preparation of a macromonomer of the structure 1 where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-(4'-hydroxybenzophenone), and DP.sub.n =10.
The procedure of Example 32 is followed, where the endcapper is
4-acetoxy-4'-chlorobenzophenone (2.3 mmol), prepared by acylation
of 4-chloro-4'-hydroxybenzophenone with acetic anhydride using
Schotten Baumann conditions.
EXAMPLE 39
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-phenethylalcohol, and DP.sub.n =16.
The procedure of Example 32 is followed, where the endcapper is the
tetrahydropyranyl ether of 4-chloro-phenethyl alcohol (1.15 mmol).
Deprotection yields the hydroxy-functionalized macromonomer.
EXAMPLE 40
Preparation of a macromonomer of the structure (1) where G.sub.1 is
carbonylmorpholine, G.sub.2 through G.sub.4 are hydrogen, E is
3-aminophenyl, and DP.sub.n =16.
General Procedure I is followed, where the monomer is
N-(2,5-dichlorobenzoyl)morpholine (11.5 mmol), and the endcapper is
N-(3-chlorophenyl)succinimide (1.15 mmol). Deprotection yields the
amino-functionalized macromonomer.
EXAMPLE 41
Preparation of a macromonomer of the structure (1) where G.sub.1 is
carbonylmorpholine, G.sub.2 through G.sub.4 are hydrogen, E is
4-(2-aminoethyl)phenyl, and DP.sub.n =16.
General Procedure I is followed, where the monomer is
N-(2,5-dichlorobenzoyl)morpholine (11.5 mmol), and the endcapper is
N-2(4-chlorophenyl)ethylsuccinimide (1.15 mmol). Deprotection
yields the amino-functionalized macromonomer.
EXAMPLE 42
Preparation of a macromonomer of the structure (1) where G.sub.1 is
carbonylmorpholine, G.sub.2 through G.sub.4 are hydrogen, E is
7-amino-2-fluorenyl, and DP.sub.n =14.
General Procedure I is followed, where the monomer is
N-(2,5-dichlorobenzoyl)morpholine (11.5 mmol), and the endcapper is
2-bromo-7-N-succinimidofluorene (1.533 mmol). Deprotection yields
the amino-functionalized macromonomer.
EXAMPLE 43
Preparation of a macromonomer of the structure 1 where G.sub.1 is
carbonylmorpholine, G.sub.2 through G.sub.4 are hydrogen, E is
4-(4'-hydroxybenzophenone), and DP.sub.n =16.
General Procedure I is followed, where the monomer is
N-(2,5-dichlorobenzoyl)morpholine (11.5 mmol), and the endcapper is
4-acetoxy-4' chlorobenzophenone (1.15 mmol). Deprotection yields
the hydroxy-functionalized macromonomer.
EXAMPLE 44
Preparation of a macromonomer of the structure 1 where G.sub.1 and
G.sub.3 are phenyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-amino-5-methoxy-2-methylphenyl, and DP.sub.n =19.
General Procedure I is followed, where the monomer is
1,4-diiodo-2,5-diphenylbenzene (11.5 mmol), and the endcapper is
4-chloro-2-methoxy-5-methylphenylphthalimide (0.92 mmol).
Deprotection yields the amino-functionalized macromonomer.
1,4-Diiodo-2,5-diphenylbenzene is prepared as described in M. Hart
and K. Harada, Tetrahedron Letters, Vol. 26, No. 1, pages 29-32
(1985).
EXAMPLES 45-47: BISMALEIMIDE RIGID-ROD MACROMONOMERS
EXAMPLE 45
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-maleimidophenyl and DP.sub.n =10.
General Procedure I is followed, where the monomer is
2,5-dichlorobenzophenone (11.5 mmol), and 2.30 mmol of the
endcapper 4-chloro-(N-succinimido)benzene (prepared from
4-chloroaniline using General Procedure IV) is employed. The free
amine obtained upon deprotection as described in the general
procedure has n=10.
The amine-terminated rigid-rod macromonomer is dissolved in 25 ml
of N,N-dimethylacetamide. To this solution, 2.5 mmol of maleic
anhydride and 0.25 mols of p-toluenesulfonic acid are added. The
solution is refluxed for 12 hours and then cooled to room
temperature. The solution is poured into toluene, whereupon the
product precipitates. The product is filtered, washed with toluene,
and dried to constant weight.
EXAMPLE 46
Preparation of a macromonomer of the structure (1) where G.sub.1 is
4-phenoxybenzoyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-(4-maleimidophenoxy)phenyl and DP.sub.n =10.
General Procedure I is followed, where the monomer is
2,5-dichloro-4'-phenoxybenzophenone (11.5 mmol). 2.30 mmol of the
endcapper 4-chloro-4'-(N-succinimido)diphenyl ether is employed.
The free amine obtained upon deprotection has n=10.
The amine-terminated rigid-rod macromonomer is dissolved in 25 ml
of toluene. To this solution, 2.5 mmol of maleic anhydride and 0.25
mmol p-toluenesulfonic acid are added. The solution is refluxed for
12 hours and then cooled to room temperature. The solvent is
evaporated, and the product is washed repeatedly with 1M potassium
carbonate, followed by washing with water. The bismaleimide
macromonomer is then dried to constant weight.
The endcapper 4-chloro-4'-(N-succinimido) diphenylether is prepared
by an Ullmann ether synthesis. The reaction of 4-chlorophenol with
4-bromonitrobenzene yields 4-chloro-4'-(nitro)diphenylether.
Reduction of the nitro group under standard conditions yields the
corresponding aminochloro derivative. The succinimide is prepared
by allowing succinic anhydride to react with the aminochloro
compound in toluene, using p-toluenesulfonic acid as catalyst.
EXAMPLE 47
Preparation of a macromonomer of the structure 1 where G.sub.1 and
G.sub.3 are butoxy, G.sub.2 and G.sub.4 are H, E is
5-(2-maleimido)benzophenone, and DP.sub.n =20.
General Procedure I is followed, using 1,4-di-chloro-2,
5-dibutoxybenzene (11.5 mmol) as monomer and 1.15 mmol of the
succinimide derived from 2-amino-5-chlorobenzophenone as endcapper.
The free amine is obtained upon deprotection as described in
General Procedure V.
The monomer 1,4-dichloro-2,5-dibutoxybenzene can be obtained by
treatment of 2,5-dichlorohydroquinone (R. L. Beddoes, J. M. Bruce,
H. Finch, L. M. J. Heelam, I. D. Hunt, and O. S. Mills, J. C. S.
Perkin I, 2670, (1981).) with sodium carbonate in
N,N'-dimethylacetamide, followed by addition of approximately 2.2
equivalents of n-butanol.
The amine-terminated rigid-rod macromonomer is dissolved in 25 ml
of toluene. To this solution 1.25 mmol of maleic anhydride and 0.13
mmol p-toluenesulfonic acid are added. The solution is refluxed for
12 hours and then cooled to room temperature. The solvent is
evaporated, and the product is washed repeatedly with 1M potassium
carbonate, followed by washing with water. The product is then
dried to constant weight.
EXAMPLES 48-51: NADIMIDE RIGID-ROD MACROMONOMERS
EXAMPLE 48
Preparation of a macromonomer of the structure (1) where G.sub.1,
is benzoyl, G.sub.2 through G4 are hydrogen, E is 2-(nadimido
benzene), and DP.sub.n =16.
The amine-terminated rigid-rod macromonomer of Example 33 is
dissolved in 25 milliliters of N,N-di-methyl-acetamide. To this
solution, 2.5 mmol of cis-5-norbornene-endo-2,3-dicarboxylic
anhydride and 0.25 mmol p-toluenesulfonic acid are added. The
solution is refluxed for 12 hours and then cooled to room
temperature. The solution is poured into toluene, whereupon the
product precipitates. The product is filtered, washed with toluene,
and dried to constant weight to give the nadimide terminated
macromonomer.
EXAMPLE 49
Preparation of a macromonomer of the structure (1) where G.sub.1 is
4-phenoxybenzoyl, G.sub.2 through G.sub.4 are H, E is
2-(4'-nadimidobenzophenone), and DP.sub.n =10.
General Procedure I is followed, where the monomer is
4'-phenoxy-2,5-dichlorobenzophenone (11.5 mmol), and 2.30 mmol of
the endcapper 2-chloro-4'-(N-succini-mido) benzophenone is
employed. The free amine obtained upon deprotection has n=10.
The amine-terminated rigid-rod macromonomer is dissolved in 25 ml
of N,N-dimethylacetamide. To this solution, 2.5 mmol of
cis-5-norbornene-endo-2,3-di-carboxylic and 0.25 mols of
p-toluenesulfonic acid are added. The solution is refluxed for 12
hours and then cooled to room temperature. The solution is poured
into toluene, whereupon the product precipitates. The product is
filtered, washed with toluene, and dried to constant weight.
EXAMPLE 50
Preparation of a macromonomer of the structure (1) where G.sub.1
and G.sub.3 are butoxy, G.sub.2 and G.sub.4 are H, E is
5-(2-nadimido)benzophenone, and DP.sub.n =20.
The amine-terminated rigid-rod macromonomer of Example 47 is
dissolved in 25 ml of N,N-dimethyl-acetamide. To this solution,
1.13 mmol cis-5-norbor-nene-endo-2, 3-dicarboxylic anhydride and
0.13 mmol p-toluenesulfonic acid are added. The solution is
refluxed for 12 hours and then cooled to room temperature. The
solution is poured into toluene, whereupon the product
precipitates. The product is filtered, washed with toluene, and
dried to constant weight.
EXAMPLE 51
Preparation of a macromonomer of the structure (1) where G.sub.1 is
4-phenoxybenzoyl, G.sub.2 through G.sub.4 are H, E is
2-(4'-nadimido)benzophenone, and DP.sub.n =20.
General Procedure I is followed, where the monomer is
2,5-dichloro-4'-phenoxybenzophenone (11.5 mmol) and 1.15 mmol of
the endcapper 2-chloro-4'-(N-succini-mido) benzophenone is
employed. The free amine obtained upon deprotection as described in
Example 1 has n=20.
The amine-terminated rigid-rod macromonomer is dissolved in 25 ml
of N,N-dimethylacetamide. To this solution, 1.13 mmol
cis-5-norbornene-endo-2,3-di-carboxylic anhydride and 0.13 mmol
p-toluenesulfonic acid are added. The solution is refluxed for 12
hours and then cooled to room temperature. The solution is poured
into toluene, whereupon the product precipitates. The product is
filtered, washed with toluene, and dried to constant weight.
EXAMPLES 52-55: BENZOCYCLOBUTENE RIGID-ROD MACROMONOMERS
EXAMPLE 52
Preparation of a macromonomer of the structure (1) where G.sub.1 is
carbophenoxy (-(CO)OC.sub.6 H.sub.5) G.sub.2 through G.sub.4 are H,
E is 4-benzocyclobutene, and DP.sub.n =10.
General Procedure I is followed, where the monomer is
2,5-dichlorophenylbenzoate (11.5 mmol) (prepared by benzoylation of
2,5-dichlorophenol with benzoyl chloride using Schotten Baumann
conditions) and 2.3 mmol of the endcapper 4-chlorobenzocyclobutene
is employed. The endcapper 4-chlorobenzocyclobutene is obtained
from the commercially available monosodium salt of 4-chlorophthalic
acid. Reduction to the dibenzyl alcohol using lithium aluminum
hydride in refluxing tetrahydrofuran, followed by treatment with
phosphorous tribromide in refluxing toluene, yields the dibenzyl
obromide. Treatment of this compound with disodium sulfide in
refluxing 95% ethanol yields 4-chloro-benzotetrahydrothiophene.
This compound is treated with peracetic acid to yield the
corresponding sulfone. Pyrolysis of this sulfone in vacuo yields
4-chlorobenzocyclobutene [reference to synthesis: M. P. Cava and A.
A. Deana, JACS 81, 4266 (1959)].
EXAMPLE 53
Preparation of a macromonomer of the structure (1) where G.sub.1
and G.sub.2 form a bridging group -CHCHCHN-, G.sub.3 and G.sub.4
are H, E is 4-benzocyclobutene, and DP.sub.n =10.
General Procedure I is followed, where the monomer is
5,8-dichloroquinoline (11.5 mmol) [reference to synthesis: M.
Gordon and D. E. Pearson, J. Org. Chem., 29, 329 (1964)], and 2.3
mmol of the endcapper 4-chlorobenzocyclobutene is employed.
EXAMPLE 54
Preparation of a macromonomer of the structure 2 where A.sub.1 and
A.sub.2 are N, G.sub.1 and G.sub.2 are nil, G.sub.3 and G.sub.4 are
H, E is 4-benzocyclobutene, and DP.sub.n =6.
General Procedure I is followed, where the monomer is commercially
available 3,6-dichloropyridazine (11.5 mmol), and 3.8 mmol of the
endcapper 4-chlorobenzo-cyclobutene is employed.
EXAMPLE 55
Preparation of a macromonomer of the structure (1) where G.sub.1 is
carbonylpiperidine, G.sub.2 through G.sub.4 are H, E is
4-benzocyclobutenemethane, and DP.sub.n =20.
General Procedure I is followed, where the monomer is
N-(2,5-dichlorobenzoyl)piperidine (11.5 mmol) and 1.15 mmol of the
endcapper 4-iodomethylbenzocyclobutene is employed.
The endcapper 4-iodomethylbenzocyclobutene can be obtained by first
esterifying commercially available 3,3-dimethylbenzoic acid with
ethanol, using HCl as a catalyst. The corresponding ethyl ester
derivative is treated with N-bromosuccinimide to yield the dibenzyl
bromide. Treatment of this compound with disodium sulfide in
refluxing 95% ethanol yields
ethylbenzo-tetrahydro-thiophene-4-carboxylate. This compound is
treated with peracetic acid to yield the corresponding sulfone.
Pyrolysis of this sulfone in vacuo leads to
ethylbenzocyclobutene-4-carboxylate [ref. M. P. Cava and A. A.
Deana, JACS 81, 4266 (1959)]. This ethyl ester is reduced to the
corresponding benzyl alcohol with lithium aluminum hydride in THF.
The benzyl alcohol is treated with p-toluenesulfonyl chloride in
pyridine at room temperature to form the corresponding sulfonate
ester. This compound, when treated with sodium iodide in acetone,
yields 4-iodomethylbenzocyclobutene.
EXAMPLES 56-58: BIPHENYLENE-TERMINATED MACROMONOMERS
EXAMPLE 56
Preparation of a macromonomer of the structure (1) where G.sub.1 is
carbonylmorpholine, G.sub.2 through G.sub.4 are H, E is
2-biphenylene and DP.sub.n =10.
General Procedure I is followed, where the monomer is
N-(2,5-dichlorobenzoyl)morpholine (11.5 mmol), and 2.30 mmol of the
endcapper 2-chloro-biphenylene is employed.
The endcapper 2-chlorobiphenylene is prepared from the
corresponding 2-aminobiphenylene [Reference to synthesis: W.
Vancraeynest and J. K. Stille, Macromolecules, 13, 1361 (1980)].
The amine is first converted to 2-diazobiphenylene by treatment
with nitrous acid, followed by addition of cuprous chloride, which
results in formation of 2-chlorobiphenylene (Sandmeyer
reaction).
EXAMPLE 57
Preparation of a macromonomer of the structure (1) where G.sub.1 is
phenyl, G.sub.1 through G.sub.4 are H, E is 2-bipheny-lene, and
DP.sub.n =20.
General Procedure I is followed, where the monomer is
2,5-dichlorobiphenyl (11.5 mmol). 1.15 mmol of the endcapper
2-chlorobiphenylene is employed, yielding a biphenylene-terminated
rigid-rod macromonomer.
The monomer 2,5-dichlorobiphenyl is prepared by treating
dichlorobenzene with 75% dibenzoyl peroxide (25% water) for 2.5
hours from 100.degree. C. to 140.degree. C. The product is isolated
by distillation under reduced pressure [H. T. Land, W. Hatke, A.
Greiner, H. W. Schmidt, W. Heitz, Makromol. Chem., 191, 2005
(1990)].
EXAMPLE 58
Preparation of a macromonomer of the structure (1) where G.sub.1 is
phenyl, G.sub.1 through G.sub.4 are H, E is 2-bipheny-lene, and
DP.sub.n =20.
General Procedure I is followed, as in Example 29; 1.15 mmol of the
endcapper 2-chlorobiphenylene is employed, and the resulting
biphenylene terminated rigid-rod macromonomer has structure 1 where
G.sub.1 is benzoyl, the remaining G's are H, E is 2-biphenylene and
n=20.
EXAMPLE 59: ACETYLENE TERMINATED MACROMONOMERS
EXAMPLE 59
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are H, E is ethynyl, and DP.sub.n
=10.
To the monomer of Example 11 (4.2 g, 1 mmol) in 25 ml of anisole
(cooled to 0.degree. C.) is added lithium diisopropylamine (LDA) (2
mmol) and diethyl chlorophosphate (2 mmol). The reaction mixture is
warmed to room temperature and additional LDA (2.2 mmol) is added.
After 4 hours, the mixture is poured into 100 ml of ethanol and the
precipitate is filtered, washed with 25 ml of ethanol, and
dried.
EXAMPLES 60-62: EPOXIDE-TERMINATED MACROMONOMERS
EXAMPLE 60
Preparation of a macromonomer of the structure (1) where G.sub.1 is
carbonylmorpholine, G.sub.2 through G.sub.4 are H, E is 4-styrene
oxide, and DP.sub.n is 15.
General Procedure I is followed, where the monomer is
N-(2,5-dichlorobenzoyl)morpholine (11.5 mmol), and 1.53 mmol of the
endcapper 4-chlorobenzaldehyde is employed. Upon isolation of the
aldehyde-terminated rigid-rod macromonomer, conversion to the
styrene oxide-terminated [e.g., bis(epoxide)] macromonomer is
carried out by treating the bis(aldehyde) with dimethylsulfonium
methylide. This is accomplished by first preparing the anion of
dimethyl sulfoxide (DMSO) by treatment with 1.68 mmols of sodium
hydride at 80.degree. C. At room temperature, this solution is
diluted with tetrahydrofuran, cooled to 5.degree. C., and 1.68
mmols of trimethylsulfonium iodide added to form dimethylsulfonium
methylide. This solution is then added by syringe to a solution of
the bis(aldehyde) macromonomer dissolved in methylene chloride [E.
J. Corey and M. Chaykovsky, Journal of the American Chemical
Society, 87, 1345 (1965); also Ibid, page 1353.]
The product bis(epoxide) rigid-rod macromonomer is isolated by
precipitation into water. Soxhlet extraction of the product with a
90:10 mixture of water/triethylamine for 24 hours yields the
purified bis(epoxide).
EXAMPLE 61
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are H, E is
4-(1,2-epoxyethylphenoxy)phenyl and DP.sub.n is 10.
General Procedure I is followed, where the monomer is
2,5-dichlorobenzophenone (11.5 mmol). 2.3 mmol of the endcapper
3-(4-chlorophenoxy)-benzaldehyde is employed. Upon isolation of the
aldehyde-terminated rigid-rod macromonomer, conversion to the
bis(epoxide) macromonomer is carried out by treating the
bisialdehyde) with dimethylsulfonium methylide, as described in the
preceding example.
EXAMPLE 62
Preparation of a macromonomer of the structure (1) where G.sub.1
and G.sub.3 are methyl, G.sub.2 and G.sub.4 are H, E is
4-N,N-bis(2,3-epoxypropyl)aminophenyl, and DP.sub.n =6.
General Procedure I is followed, where the monomer is
2,5-dichloro-p-xylene (11.5 mmol) and 3.8 mmol of the endcapper
4-(N-succinimido)chlorobenzene is employed. The free amine obtained
upon deprotection as described in General Procedure V has n=6.
The amine-terminated rigid-rod macromonomer is suspended in 25 ml
of dichloromethane (or, alternatively, triethylamine), and 4.0
mmols of epichlorohydrin is added. The solution is allowed to stir
for two hours at room temperature, at which time the bis(epoxide)
rigid-rod macromonomer is isolated by pouring into a solution of
water/triethylamine in a 90:10 ratio. The precipitated macromonomer
is further purified by Soxhlet extraction with a 90:10
water/triethylamine solution for 24 hours.
EXAMPLE 63
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is 5-veratryl, and
DP.sub.n =25.
Anhydrous nickel(II) chloride (50 mg, 0.39 mmol),
triphenylphosphine (750 mg, 2.86 mmol), sodium iodide (150 mg, 1.0
mmol), and 325 mesh activated zinc powder (1.2 g, 18 mmol) are
placed into a 25 ml flask under an inert atmosphere along with 5 ml
of anhydrous N-methylpyrrolidinone (NMP). This mixture is stirred
at 50.degree. C. for about 10 minutes, leading to a deep-red
coloration. A solution of 11.5 mmol of monomer in 10 ml of
anhydrous NMP is then added by syringe. After stirring for 10
hours, 0.92 mmol 5-bromoveratraldehyde is added to the resulting
viscous solution, which is stirred for an additional 10 hours. The
solution is then poured into 100 ml of 1 molar hydrochloric acid in
ethanol to dissolve the excess zinc metal and to precipitate the
macromonomer. This suspension is filtered and the precipitate
triturated with acetone, and dried to afford a light tan to white
powder, in nearly 100% yield. The aldehyde function of the veratryl
end groups may then be reduced to a hydroxymethyl group.
Alternatively the aldehyde group may be converted into an
aminomethyl group by forming the Schiff's base with ammonia or a
primary or secondary amine, followed by reduction.
EXAMPLE 64
Preparation of a macromonomer of the structure (1) where G.sub.1 is
benzoyl, G.sub.2 through G.sub.4 hydrogen, E is -NH.sub.2, and
DP.sub.n =50.
Anhydrous nickel(II) chloride (0.4 mmol), triphenylphosphine (750
mg, 2.86 mmol), sodium iodide (150 mg, 1.0 mmol), and 325 mesh
activated zinc powder (1.2g, 18 mmol) are placed into a 25 ml flask
under an inert atmosphere along with 5 ml of anhydrous
N-methyl-pyrrolidinone (NMP). This mixture is stirred at 50.degree.
C. for about 10 minutes, leading to a deep-red coloration. A
solution of 10 mmol of monomer in 10 ml of anhydrous NMP is then
added by syringe. After stirring for 10 hours, the reaction is
quenched with 10 mmol sodamide in 1 ml NMP and stirred for an
additional hour. The solution is then poured into 100 ml of 1 molar
hydrochloric acid in ethanol to dissolve the excess zinc metal and
precipitate the macromonomer. This suspension is filtered and the
precipitate triturated with acetone, and dried to afford a light
tan to white powder, in nearly 100% yield.
EXAMPLE 65
Preparation of a macromonomer of the structure (1), where G.sub.1
is benzoyl, G.sub.2 through G.sub.4 are hydrogen, E is carboxy, and
DP.sub.n =20-25.
Anhydrous nickel(II) chloride (50 mg, 0.39 mmol),
triphenylphosphine (750 mg, 2.86 mmol), sodium iodide (175 mg, 1.17
mmol), and 325 mesh activated zinc powder (0.5-1.0 g, 7.5-15 mmol)
are placed into a 25 ml flask under an inert atmosphere along with
7 ml of anhydrous N-methylpyrrolidinone (NMP). This mixture is
stirred at 50.degree. C. for about 10-20 minutes, leading to a
deep-red coloration. A solution of 2,5-dichlorobenzophenone (1.1 g,
4.38 mmol) in 8 ml of anhydrous NMP is then added all at once by
syringe. After a period of about 20 minutes, the reaction is
pressurized with carbon dioxide. After stirring for about 24 hours,
the resulting viscous solution is poured into 100 ml of 1 molar
hydrochloric acid in ethanol to hydrolyze the metal carboxylate
derivative, dissolve the excess zinc metal and precipitate the
macromonomer. This suspension is filtered and the precipitate
triturated with acetone and dried to afford the carboxy-terminated
macromonomer.
EXAMPLE 66
Preparation of a macromonomer of the structure (1) where G.sub.1 is
OH, G.sub.2 through G.sub.4 are hydrogen, E is 3-benzaldehyde, and
DP.sub.n =40.
The Grignard reagent of 2,5-dibromophenol-tetra-hydropyranylether,
is prepared by addition of 2,5-dibromophenol-tetrahydropyranylether
(50 mmol) to magnesium turnings, 50 mmol, in dry tetrahydrofuran
(THF). Upon completion of the reaction, 2.5 mmol
2-(3-bromophenyl)-1,3-dioxolane is added, followed by 0.1 mmol of
bis(triphenylphosphine)nickel(II) chloride. The solution is heated
to reflux for 6 hr. The polymer is precipitated by addition of the
cooled solution to dilute acid.
EXAMPLE 67
Preparation of a macromonomer of the structure (1) where G.sub.1
and G.sub.3 are phenyl, G.sub.2 through G.sub.4 are hydrogen, E is
4-aminophenyl, and DP.sub.n =5.
A mixture of 4-bromo-2,5-diphenylbenzeneboronic acid (10 mmol),
4-amino-benzeneboronic acid (2 mmol), tetrakis (triphenylphosphine)
palladium (0.1 mmol), benzene (50 ml) and aqueous Na.sub.2 CO.sub.3
(2M, 40 ml) are refluxed and stirred under N.sub.2 for 48 hours.
The mixture is then poured into acetone (250 ml) to precipitate the
macromonomer.
4-Bromo-2,5-diphenylbenzeneboronic acid is prepared as follows: A
solution of n-butyllithium (1.6 M, 15 ml) in hexane is added slowly
to a cooled (-40.degree. C.) solution of
1,4-di-bromo-2,5-diphenylbenzene (25 mmol) in diethylether (100
ml). This mixture is allowed to warm to room temperature and is
stirred for 2 hours. This solution is transferred into a dropping
funnel and added to a cooled (-60.degree. C.) solution of
trimethylborate (74 mmol) in ether (200 ml). It is then stirred for
8 hours at room temperature. After hydrolysis with aqueous HCl (2M,
150 ml), the layers are separated and the aqueous layer is
extracted with ether (100 ml). The solvent is then removed from the
combined organic layers and water (5 ml) and petroleum ether (100)
are added. The precipitate is recovered by filtration, and
recrystallized from toluene.
EXAMPLES 68-82: POLYMERS INCORPORATING RIGID-ROD MACROMONOMERS
EXAMPLE 68
A solution of the macromonomer of Example 39 (1 mmol, 2.76 g),
hexamethylenediamine (99 mmol, 11.505 g), and pyridine (20 ml) in
150 ml NMP is added to a solution of terepthaloyl chloride (100
mmol, 20.302 g) in 50 ml NMP. The solution is warmed to 50.degree.
C. for 4 hours, then poured into water to precipitate the
copolymer. The resulting
polyhexamethyleneadipamide-co-poly-2,5-benzo-phenone is
approximately 10% by weight rigid-rod.
EXAMPLE 69
The procedure for preparation of bisphenol-A polycarbonate given in
Macromolecular Synthesis, J. A. Moore, Ed., John Wiley & Sons;
New York; 1977, Collective Vol. 1, pp 9-12 (incorporated herein by
this reference); is followed, except that 2 g of the macromonomer
of Example 38 is added along with the bisphenol-A. More
specifically, a 500 ml four-necked flask (or resin pot) equipped
with a stirrer, thermometer, a wide bore gas inlet tube, and a gas
outlet is charged with 22.8 g (0.10 mol) of bisphenol-A, 2 g of the
macromonomer of Example 38, and 228 ml of pyridine. Phosgene at a
rate of 0.25 g/min. is passed into the rapidly stirred reaction
mixture, which is maintained at 25.degree.-30.degree. C. with a
water bath. Pyridine hydrochloride will begin to separate from the
reaction mixture after about 25 minutes. This is an indication that
the reaction is about 60 percent completed. Approximately 15
minutes later, a marked increase in viscosity will be noted over a
period of 2-3 minutes; the polymerization is then essentially
completed. The copolymer may be precipitated directly in the
reaction flask and is approximately 9 percent by weight
rigid-rod.
EXAMPLE 70
The procedure for preparation of phenol-formaldehyde resin given in
Macromolecular Synthesis, J. A. Moore, Ed., John Wiley & Sons;
New York; 1977, Collective Vol. 1, pp 211-213 (incorporated herein
by this reference), is followed, except that 893 g of phenol is
used, and 30 g of the macromonomer of Example 38 is added along
with the phenol. More specifically, a 3 L three-necked round bottom
flask (or resin pot) equipped with a Teflon or stainless steel
paddle-type stirrer, thermometer, efficient bulb-type reflux
condenser, and heating mantle is charged with 893 g (9.5 mol) of
phenol (99 percent purity), 70 g (0.75 mol) of aniline, 30 g
(0.0163 mol) of the macromonomer of Example 38, 1,130 g of 37.2
percent formaldehyde solution (14 mols) and 110 g of a 28.5 percent
hot water solution of barium hydroxide octahydrate. The pressure is
reduced to 300-350 torr and the reactants are heated slowly to a
reflux temperature of 80.degree. C. and maintained there for 15
min. The reflux condenser is then replaced with a condenser set for
distillation, and the resin is dehydrated at 10-20 torr to a final
temperature of 80.degree.-90.degree. C. As the dehydration
proceeds, the molecular weight and viscosity of the condensate
increase progressively, and the resin becomes increasingly
sensitive to further heating. When the "gel time," as determined by
the so-called stroke cure test, falls to 65-85 sec., the apparatus
is quickly disassembled and the resin is poured in a thin layer
into a large shallow vessel covered with heavy aluminum foil to
provide rapid cooling. The resulting resin is approximately 5% by
weight rigid-rod.
EXAMPLE 71
The procedure for preparation of polyethylene terephthalate given
in Macromolecular Synthesis, J. A. Moore, Ed., John Wiley &
Sons; New York; 1977, Collective Vol. 1, pp 17-21 (incorporated
herein by this reference), is followed, except that 3 g of the
macromonomer of Example 5 is added to the charge along with the
ethylene glycol. More specifically, a glass "polymer tube" about 25
mm by 250 mm, sealed to a 10 mm by 70 mm neck carrying a side arm
for distillation is charged with 13.6 g (0.07 mol) of dimethyl
terephthalate (DMT), 3 g of the macromonomer of Examiner 5, 10 g
(8.8 ml, 0.16 mol) of ethylene glycol, 0.022 g (0.15% based on DMT)
of calcium acetate dihydrate, and 0.005 g (0.035% based on DMT) of
antimony trioxide. The charge is melted by submerging the tube
about half way in the vapors of boiling ethylene glycol
(197.degree. C.), and a fine capillary connected to nitrogen under
pressure, is introduced through the neck of the tube. A vacuum
tight seal is made with a piece of heavy walled rubber tubing, well
lubricated with silicone grease. The capillary must be adjusted to
reach the very bottom of the polymer tube. Methyl alcohol distills
rapidly for a few minutes. After one hour, the tube is adjusted to
be heated as completely as possible by the glycol vapors, and
heating at 197.degree. C. is continued for two hours more. The
polymer tube is then transferred to a 222.degree. C. (methyl
salicylate) vapor bath for 15 minutes, during which time excess
glycol distills and polymerization begins.
The side arm of the polymer tube is then connected by means of a
short piece of heavy walled tubing to a receiver having a side arm
for collection under vacuum. The tube is heated at 283.degree. C.
(dimethyl phthalate). Polymerization proceeds and glycol distills
slowly. After 5 to 10 minutes vacuum is applied very cautiously and
the pressure is brought to 0.2 torr or less in about 15 minutes.
Polymerization should be complete within 3 hours. The tube is then
filled with nitrogen, removed from the vapor bath and allowed to
cool. The glass is cracked away from the mass of polymer by
wrapping it in a towel and tapping with hammer. The last of the
glass, which adheres very tenaciously, must be removed with a
coarse file.
The resulting copolymer is approximately 15% by weight
rigid-rod.
EXAMPLE 72
The procedure of Padaki, Norris, and Stille for the preparation of
poly [2,2'-(p,p'-oxydipheny-lene)-6,
6'-oxy-bis(4-phenylquinoline)], given in Macromolecular Synthesis;
J. A. Moore, Ed., John Wiley & Sons; New York; 1985, Vol. 9,
pp. 53-55 (incorporated herein by this reference), is followed,
except that 0.2797 g of 4,4'-diacetyldiphenyl ether is used along
with 0.7500 g of the diacetyl-substituted macromonomer of Example
11 (with molecular weight of about 4200). More specifically, a
mixture of 0.5223 g (1.279 mmol) of 4,4'-diamino-3,
3'-dibenzoyldiphenyl ether, 0.2797 g (1.100 mmol) of
4,4'-diacetyldiphenyl ether, 0.7500 g (0.179 mmol) of the
diacetyl-substituted macromonomer of Example 11 (with molecular
weight of about 4200), 8.8 g (32 mmol) of di-m-cresyl phosphate,
and 1.5 g (14 mmol) of distilled m-cresol is stirred in a
three-neck polymerization flask equipped with a nitrogen inlet, an
overhead stirrer and a nitrogen outlet. The reaction mixture is
flushed with nitrogen for about 5 minutes and then heated in an oil
bath from room temperature to 135.degree. C. to 140.degree. C. in
about 30 minutes. It is maintained at this temperature for 48 hours
under a static nitrogen atmosphere. The resulting clear, highly
viscous solution is poured slowly into a stirred solution of 500 ml
of ethanol containing 50 ml of triethylamine to yield an off-white
fibrous material. This fibrous polymer is suspended in a small
amount (about 50 ml) of ethanol containing 10% v/v of
triethylamine, chopped in a blender and collected by filtration.
The polymer is continuously extracted for 24 hours in a Soxhlet
apparatus with ethanol containing 10% v/v triethylamine. It is then
air dried and then further dried at 110.degree. C. and 0.1 torr for
4 hours. The polymer is redissolved in 30 ml of chloroform and
reprecipitated by slow addition to a stirred solution of 300 ml of
ethanol containing 30 ml of triethylamine. The precipitated fibrous
polymer is suspended in about 50 ml of ethanol containing 5 ml of
triethylamine, chopped in a blender, collected by filtration, air
dried, and then dried further at 110.degree. C. and 0.1 torr for 24
hours to yield the copolymer, which is approximately 50% by weight
rigid rod.
EXAMPLE 73
The procedure of Wynn, Glickman, and Chiddix for the preparation of
4-nylon, given in Macromolecular Synthesis; J. A. Moore, Ed., John
Wiley & Sons; New York; 1977, Coll. Vol. 1, pp. 321-323
(incorporated herein by this reference), is followed, except that
10 g of the ester-substituted macromonomer of Example 4 is added
just prior to the addition of silicon tetrachloride. More
specifically, a 250 ml 3-necked round bottom flask equipped with
stirrer, thermometer and Claisen head suitable for vacuum
distillation is charged with a 120 g of freshly distilled
2-pyrrolidone. The charge is heated under nitrogen to 80.degree. C.
with a Glas-Col mantel. Flake potassium hydroxide (97%) (3.4 g) is
added. The water formed, together with about 20 ml of monomer, is
rapidly distilled from the flask at 1 torr. The hot solution is
rapidly transferred to an 8 oz. polyethylene bottle previously
purged with nitrogen. Ten g of the ester-substituted macromonomer
of Example 4 is then added followed by 0.5 g of silicon
tetrachloride. The bottle is capped, agitated by hand, and allowed
to cool to room temperature. After 10 minutes and at a temperature
of about 50.degree. C., polymerization is indicated by
precipitation of solid polymer. After 24 hours at room temperature,
the mixture is very hard. It is broken with a hammer and the bottle
is cut open for its removal. The lumps are then blended with a 150
ml of water containing 0.1% formic acid in a blender. The powdered
product is filtered and washed in the filter with 150 ml of 0.1%
formic acid followed by three 100 ml washings with distilled water.
It is finally washed with alcohol and dried at 3 torr at 70.degree.
C. The resulting resin is approximately 10-15% by weight
rigid-rod.
EXAMPLE 74
The procedure of Conciatori and Chenevey for the preparation of
poly [2,2'-(m-phenylene)-5,5'-bibenzimidazole], given in
Macromolecular Synthesis; J. A. Moore, Ed., John Wiley & Sons;
New York; 1977, Coll. Vol. 1, pp. 235-239 (incorporated herein by
this reference), is followed, except that 38.836 g of DPIP is used
along with 15.06 g of the ester-substituted macromonomer of Example
31 (with molecular weight of about 5020). More specifically, a
two-stage polymerization is carried out. For the first stage, a 1
liter, 3 necked flask is charged with 26.784 g (0.125 mol) of
purified 3,3'-diaminobenzidine (DAB), 38.836 g (122 mmol) of
diphenyl isophthalate (DPIP), and 15.06 g (3 mmol) of the
ester-substituted macromonomer of Example 31 (with molecular weight
of about 5,020). The flask is immersed in an oil bath and is
equipped with a stirrer, Dean-Stark trap with condenser, and a
nitrogen purge throughout the whole system. Degassing of the
reactants and system is done by alternately evacuating with a
vacuum pump and filling with nitrogen. A flow of nitrogen of about
100 ml per minute is begun and maintained throughout the
reaction.
The reaction is stirred and heating is begun at a rate of about
2.degree. C. per minute. Reaction commences at about 215.degree. C.
to 225.degree. C. Phenol and water collect in the Dean-Stark trap.
As the temperature increases and reaction proceeds, the mass
becomes so stiff that stirring is impossible. The stirring should
be stopped when the temperature reaches 250.degree. C. to
255.degree. C. and about 15 ml of condensate has been collected.
After the stirrer is stopped, the mass foams and fills the flask
about three quarters full. The polymer is heated to 290.degree. C.
and is held there for 1.5 hours. About 22 ml of condensate is
recovered.
On cooling, the friable prepolymer is removed from the flask and is
crushed.
For the second stage of polymerization, the prepolymer is charged
into a flask and degassed in the same manner as in the first stage.
A nitrogen sweep of 60 to 120 ml per minute is used throughout the
second stage. After immersion of the reactor in a heating bath, the
temperature is raised at a rate of about 1.50 per minute from
220.degree. C. to 385.degree. C. Polymerization is continued at
385.degree. C. for three hours. After cooling and removal from the
flask, a granulated copolymer that is about 28% by weight rigid-rod
is recovered.
EXAMPLE 75
The procedure of Hart for the preparation of poly(methyl
methacrylate), given in Macromolecular Synthesis; J. A. Moore, Ed.,
John Wiley & Sons; New York; 1977, Coll. Vol. 1, pp. 23-25
(incorporated herein by this reference), is followed, except that 1
g of the acrylyl-substituted macromonomer of Example 29 is added as
a comonomer. A three-liter three-necked flask is charged with 1.5
liters of distilled water, 15 grams of Cyanamer A-379 (a water
soluble modified polyacrylamide resin available from American
Cyanamid Company as a free-flowing powder), 8.5 grams of disodium
phosphate (Na.sub.2 HPO.sub.4), and 0.5 gram of monosodium
phosphate (NaH.sub.2 PO.sub.4). The flask is fitted with a
thermometer, a condenser, and a glass stirrer of the half-moon
type; the mixture is warmed to 30.degree.-35.degree. C. and stirred
until a clear solution is obtained.
In a one liter beaker are mixed 500 grams of distilled methyl
methacrylate, one gram of the acrylyl-substituted macromonomer of
Example 29, and 5 grams of benzoyl peroxide. When the peroxide has
been completely dissolved, the solution is added to the flask. The
half-moon paddle is adjusted to about one-half inch below the top
surface, and agitation is begun at about 400 rpm. The reactor is
flushed lightly with nitrogen gas for one to two minutes to remove
atmospheric oxygen. The agitator speed is adjusted to 250 rpm, and
the reaction mixture is heated to 76.degree.-78.degree. C. This
temperature is maintained for 2.5 to 3 hours. After the mixture is
cooled to room temperature, the polymer is recovered by filtration
in a Buchner funnel. The polymer is washed several times with water
and dried at 65.degree. C. for 5-10 hours. The resulting copolymer
is approximately 6% by weight rigid-rod.
EXAMPLE 76
In a flamed 500 ml nitrogen flask equipped with a magnetic stirrer,
8.647 g (42.59 mmol) of isophthaloyl dichloride, 10,000 g (43.81
mmol) of bisphenol-A, 5.000 g (1.22 mmol) of the
chlorocarbonyl-substituted macromonomer prepared by reacting the
carboxy-terminated macromonomer of Example 65 with thionyl
chloride, 100 ml of 1,1,2,2-tetrachloroethane and 15 ml of pyridine
are added under nitrogen pressure and heated at 120.degree. C. for
20 hours. The copolymer is precipitated in methanol, filtered,
redissolved in chloroform, reprecipitated in methanol, filtered,
and dried at 80.degree.-100.degree. C. i.vac. The resulting
copolymer is approximately 25% by weight rigid-rod.
EXAMPLE 77
The epoxy-terminated macromonomer of Example 62 (45 g) is mixed
with the diglycidyl ether of bisphenol-A (EPON 825, commercially
available from Shell Chemical Co.) to form Part I of a two-part
epoxy. Part II is formed using triethylene tetramine (TETA) as a
curing agent. The cured epoxy resin is formed by mixing TETA (12.8
g) with Part I (100 g).
EXAMPLE 78
A mixture consisting of the ester-functionalized macromonomer of
Example 7 (5 g) and poly-e-caprolactam (95 g) is heated to about
240.degree. C. and mixed until well blended. Under these
conditions, the macromonomer is chemically incorporated into the
polyamide via transamination. The resulting copolymer is
approximately 5% by weight rigid-rod.
EXAMPLE 79
A mixture consisting of the ester-functionalized macromonomer of
Example 7 (5 g) and polyethylene terephthalate (95 g) is heated to
about 260.degree. C. and mixed until well blended. Under these
conditions, the macromonomer is chemically incorporated into the
polyester via transesterification. The resulting copolymer is
approximately 5% by weight rigid-rod.
EXAMPLE 80
A mixture consisting of the hydroxy-functionalized macromonomer of
Example 38 (5 g), bisphenol-A polycarbonate (95 g), and lithium
stearate (0.05 g) is heated to about 280.degree. C. and mixed until
well blended. Under these conditions, the macromonomer is
chemically incorporated into the polycarbonate via
transesterification. The resulting copolymer is approximately 5% by
weight rigid-rod.
EXAMPLE 81
A mixture of the ester functionalized macromonomer of Example 4
(0.65 g), caprolactam (13 g) and 0.5 g of 50% aqueous aminocaproic
acid as the catalyst was heated in a nitrogen purged tube for about
4-6 hours at approximately 280.degree. C. in a sand bath and then
allowed to cool. The copolymer, which is approximately 5-10% by
weight rigid-rod, was obtained as a light yellow powder after
crushing, extracting with boiling water for about 8 hours, and
vacuum drying at 50.degree. C.
The above descriptions of exemplary embodiments of macromonomers
having functional end groups, the rigid-rod polymers, copolymers,
and resins prepared therefrom, and the processes for making same
are illustrative of the present invention. Because of the
variations which will be apparent to those skilled in the art,
however, the present invention is not intended to be limited to the
particular embodiments described above. The scope of the invention
is defined in the following claims.
* * * * *